WorldWideScience

Sample records for racemic zeolite-type zincophosphate

  1. A New Organo-templated Layered Zincophosphate Synthesized from a Solvothermal System Containing Racemic1,2-Diaminopropane

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new layered zincophosphate was synthesized under solvothermal conditions by employing racemic 1,2-diaminopropane as the structure-directing agent. The structure of the compound was solved by means of single-crystal X-ray diffraction analysis. It crystallized in the monoclinic space group P21/c (No. 14) with a=1.047 0(3) nm, b=0.787 31(18) nm, c=0.662 68(16) nm, β=103.120(5)°, V=0.532 0(2) nm3 and Z=4. The structure is made up of anionic zincophosphate sheets stacked in an AAAA sequence. The individual sheet contains three- and four-membered rings and the infinite Zn-O-Zn chains can also be envisaged in the sheet. The charge-balancing diprotonated racemic 1,2-diaminopropane cations are sandwiched between the layers, whereas the inorganic layers are stabilized by strong H-bonds formed between the N atoms of the amine and the O atoms in the inorganic sheets.

  2. Thermochemical Study on the Chiral Sodium Zincophosphate Nanocrystalline

    Institute of Scientific and Technical Information of China (English)

    WU, Jian; YUAN, Ai-Qun; HUANG, Zai-Yin; SONG, Bao-Lin; LIAO, Sen

    2006-01-01

    Chiral sodium zincophosphate nanocrystalline has been prepared and characterized. The standard molar enthalpy of the following reaction 12Na3PO4·12H2O(s) + 12ZnSO4·7H2O(s) = Na12(Zn12P12O48)·12H2O(s) +12Na2SO4(s)+216H2O(1) was determined by solution reaction calorimetric at 298.15 K, and calculated to be 33.666+0.195 kJ/mol. From the results and other auxiliary quantities, the standard enthalpy of formation for sodium zincophosphate nanocrystalline was derived to be AfHmΘ [Na12(Zn12P12O48)·12H2O(s), 298.15 K]=-24268.494t0.815 kJ/mol.

  3. Racemic DNA crystallography.

    Science.gov (United States)

    Mandal, Pradeep K; Collie, Gavin W; Kauffmann, Brice; Huc, Ivan

    2014-12-22

    Racemates increase the chances of crystallization by allowing molecular contacts to be formed in a greater number of ways. With the advent of protein synthesis, the production of protein racemates and racemic-protein crystallography are now possible. Curiously, racemic DNA crystallography had not been investigated despite the commercial availability of L- and D-deoxyribo-oligonucleotides. Here, we report a study into racemic DNA crystallography showing the strong propensity of racemic DNA mixtures to form racemic crystals. We describe racemic crystal structures of various DNA sequences and folded conformations, including duplexes, quadruplexes, and a four-way junction, showing that the advantages of racemic crystallography should extend to DNA.

  4. Racemic protein crystallography.

    Science.gov (United States)

    Yeates, Todd O; Kent, Stephen B H

    2012-01-01

    Although natural proteins are chiral and are all of one "handedness," their mirror image forms can be prepared by chemical synthesis. This opens up new opportunities for protein crystallography. A racemic mixture of the enantiomeric forms of a protein molecule can crystallize in ways that natural proteins cannot. Recent experimental data support a theoretical prediction that this should make racemic protein mixtures highly amenable to crystallization. Crystals obtained from racemic mixtures also offer advantages in structure determination strategies. The relevance of these potential advantages is heightened by advances in synthetic methods, which are extending the size limit for proteins that can be prepared by chemical synthesis. Recent ideas and results in the area of racemic protein crystallography are reviewed.

  5. Analysis Si/Al ratio in zeolites type FAU by laser induced breakdown spectroscopy (LIBS)

    Science.gov (United States)

    Contreras, W. A.; Cabanzo, R.; Mejía-Ospino, E.

    2011-01-01

    In this work, Laser Induced Breakdown Spectroscopy (LIBS) is used to determine the Si/Al ratio of Zeolite type Y. The catalytic activity of zeolite is strongly dependent of the Si/Al ratio. We have used Si lines in the spectral region between 245-265 nm to determine temperature of the plasma generated on pelletized sample of zeolite, and stoichiometry relation between Si and Al.

  6. A Simple and Novel Route for The Preparation of Chiral Sodium Zincophosphate

    Institute of Scientific and Technical Information of China (English)

    LIAO Sen; WU Wen-Wei; SUN Ya-Bo; SONG Bao-Ling

    2008-01-01

    A simple and novel route for the preparation of chiral sodium zincophosphate (NaZnPO4·H2O) (CZP) was studied, and the target product was obtained with Na3PO4·12H2O and ZnSO4·7H2O as raw materials and polyethylene glycol-400 (PEG-400) as a surfactant via one step low heat solid state reaction.The product was characterized with TG/DTG, XRD, TEM and SEM.The experimental results showed that the NaZnPO4·H2O, which was all obtained from different P/Zn atomic ratios (0.9-1.15) of Na3PO4·12H2O to ZnSO4·7H2O and different ageing time (2.0-8.0 h) at 60 ℃, had the same chiral crystal structures except slight difference in their crystallinity.The comparison experimental results suggest that the ageing temperature and anion control the enantiomorphism of NaZnPO4·H2O,that is, if ZnSO4·7H2O or Zn(NO3)2·6H2O were used as Zn source, the first chiral structure of space group P6122 was formed when the reaction mixture was aged at 60℃,and the second chiral structure of space group P6522 was got when the reaction mixture was aged at room temperature.

  7. Racemic carbohydrates - fact or fiction?

    DEFF Research Database (Denmark)

    Senning, Alexander Erich Eugen

    2007-01-01

    Chemical Abstracts Service has developed unsound practices in the naming and handling of simple carbohydrates such as aldopentoses 1, aldohexoses 2, and ketohexoses 3. Typically, the common name glucose is sometimes, inappropriately, interpreted as meaning DL-glucose DL-2d. Thus, a considerable...... number of CA names and registry numbers have been created for non-existing racemic carbohydrates and linked to irrelevant references which, moreover, in many cases cannot be retrieved by the SciFinder Scholar program....

  8. Solid-State Synthesis of Zincophosphate with Organic Temple and Its Characterization%有机模板固相合成磷酸锌及其表征

    Institute of Scientific and Technical Information of China (English)

    王金霞; 高艳阳; 魏宁

    2011-01-01

    以1,6-己二胺作为模板剂,以ZnC12、NaH2 PO4为原料,采用固相合成法于80℃反应4h合成了含有模板晶的磷酸锌化合物3C6N2H18·Zn5H(PO4)4]2·6H2O,产物用化学分析、元素分析、红外光谱及热重分析等进行了表征.结果表明,用固相合成法能够在低温、短时间内合成磷酸锌化合物.%Using 1, 6-diaminohexane as template agent, zincophosphate compound 3C6N2H]8 ? [Zn5H (PO4)4]2 ? 6H2O was prepared through reacting at 80 T? For 4 h by solid-state synthesis method with ZnClz and NaH2PO4 as raw materials. The prouduct was characterized by IR and TG analysis. The results showed that zincophosphate compound could be synthesized by solid-state method at lower heating temperature in shorter time.

  9. Racemization of Meteoritic Amino Acids

    Science.gov (United States)

    Cohen, Barbara A.; Chyba, Christopher F.

    2000-05-01

    Meteorites may have contributed amino acids to the prebiotic Earth, affecting the global ratio of right-handed to left-handed (D/L) molecules. We calculate D/L ratios for seven biological, α-hydrogen, protein amino acids over a variety of plausible parent body thermal histories, based on meteorite evidence and asteroid modeling. We show that amino acids in meteorites do not necessarily undergo complete racemization by the time they are recovered on Earth. If the mechanism of amino acid formation imposes some enantiomeric preference on the amino acids, a chiral signature can be retained through the entire history of the meteorite. Original enantiomeric excesses in meteorites such as Murchison, which have undergone apparently short and cool alteration scenarios, should have persisted to the present time. Of the seven amino acids for which relevant data are available, we expect glutamic acid, isoleucine, and valine, respectively, to be the most likely to retain an initial enantiomeric excess, and phenylalanine, aspartic acid, and alanine the least. Were the D/L ratio initially identical in each amino acid, final D/L ratios could be used to constrain the initial ratio and the thermal history experienced by the whole suite.

  10. Enantiomeric resolution of multiple chiral centres racemates by capillary electrophoresis.

    Science.gov (United States)

    Ali, Imran; Suhail, Mohd; Al-Othman, Zeid A; Alwarthan, Abdulrahman; Aboul-Enein, Hassan Y

    2016-05-01

    Enantiomeric resolution of multichiral centre racemates is an important area as some multichiral centre racemates are of great medicinal importance. However, enantioseparation of such types of racemates is a challenging task. Amongst many analytical techniques, capillary electrophoresis is a powerful technique and may be used to resolve such racemates. Only few papers are available describing enantiomeric resolution of such racemates. Therefore, efforts have been made to describe the enantiomeric resolution of multichiral centre racemates by capillary electrophoresis. This article discusses the importance of multichiral racemates, the need for capillary electrophoresis in enantiomeric resolution and chiral resolution of multichiral centre racemates using various chiral selectors. Further, attempts have been made to discuss the future challenges and prospects of enantiomeric resolution of multichiral racemates. The various chiral selectors used for the purpose are chiral crown ether, cyclodextrins, polysaccharides, macrocyclic glycopeptide antibiotics and ligand exchange.

  11. Influence of microwave radiation on the growth of gold nanoparticles and microporous zincophosphates in a reverse micellar system.

    Science.gov (United States)

    Doolittle, John W; Dutta, Prabir K

    2006-05-09

    The water core of reverse micelles has been extensively used as the site for synthesis of a variety of materials. However, water-in-oil reverse micelles have a limited range of temperatures over which they are stable as a single phase. Directing heat to the water cores, the usual site of synthesis without heating the bulk provides added opportunities for synthesis. Microwave radiation is a method for superheating the water cores. In this study, we use an H2O-sodium bis(2-ethylhexyl) sulfosuccinate (AOT)-heptane reverse micelle system for the synthesis of Au particles by hydrazine reduction of HAuCl4 in the presence and absence of microwave radiation. The duration of the microwave radiation was limited to a 2-min duration at a power of 300 W, thereby ensuring that the reverse micelle phase is maintained during the synthesis. At all hydrazine concentrations studied (0.5-2 M), the presence of microwave radiation led to an increase in the particle size of Au. The second system examined was the growth of microporous zincophosphate-X (ZnPO-X, an analogue of the faujasite structure) synthesized from H2O-dioctyldimethylammonium chloride (DODMAC)-heptane reverse micelle system. Microwave radiation was applied for 1 min at 150 W at various stages of the nucleation and growth process, and did not disrupt the reverse micelle system. Product analysis after 48 h of reaction showed that the 1-min microwave pulse, if applied during the nucleation stage (the first 4 h), promoted the formation of NaZnPO4.H2O over ZnPO-X. The effect of the microwave pulse at the growth stage was to promote the formation of ZnPO-X. Absorption of the microwave radiation by the water core and surrounding polar surfactant molecules leads to a rapid rise in local temperature (predicted to be approximately 150 degrees C/min for the AOT system), increasing the rates of intramicellar reactions.

  12. Synthesis of zeolitic-type adsorbent material from municipal solid waste incinerator bottom ash and its application in heavy metal adsorption

    OpenAIRE

    Chiang, Yi Wai; Ghyselbrecht, Karel; Santos, Rafael; Meesschaert, Boudewijn; Martens, Johan

    2012-01-01

    Municipal solid waste incinerator (MSWI) bottom ash (BA) was converted to zeolitic-type adsorbent materials by hydrothermal conversion under strongly alkaline conditions. The conversion product was determined to be a mixture of sodium aluminum silicate hydrate (SASH) (Na2O·Al2O3·1.68SiO2·1.73H2O) and tobermorite (Ca5Si6O16(OH)2·4H2O). The BET specific surface area was 22.1 m2/g, which represented a significant gain compared to the BA (4.6 m2/g) due to the formation of micropores and mesopores...

  13. Abiotic racemization kinetics of amino acids in marine sediments.

    Science.gov (United States)

    Steen, Andrew D; Jørgensen, Bo Barker; Lomstein, Bente Aa

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5)-11×10(-5) yr(-1). These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  14. Synthesis of a Chain Aluminophosphate Containing Racemic 1, 2-Diaminopropane

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A one-dimensional chain aluminophosphate C1.5H7.5N1.5Al0.5PO4 containing diprotonated racemic 1, 2-diaminopropane cations was synthesized from an alcoholic system. The compound consists of infinite inorganic [AlP2O8] chains of alternately connected AlO4 and PO2(=O)2 tetrahedral units and the racemic template molecules. The macroanionic chains contain corner-shared double four-membered rings.

  15. Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene

    Directory of Open Access Journals (Sweden)

    Masashi Hasegawa

    2014-03-01

    Full Text Available Dissymmetric 1,3-diphenylallene derivative 3 connected with 4,5-bis(methyl-thiotetrathiafulvalenyl and 1-pyrenyl substituents was prepared and characterized. The molecular structure was determined by X-ray crystallographic analysis. Optical resolution was accomplished using a recycling chiral HPLC, and its chiroptical properties were examined with optical rotation and electronic circular dichroism (ECD spectra. The title compound underwent photoracemization under daylight. This behavior was investigated in various solvents and compared with that of 1,3-bis(tetrathiafulvalenylallene (bis-TTF-allene derivative 2. The first-order rate plot of the intensity of the ECD spectra at a given time interval gave the rate of racemization. Mild racemization was observed in polar solvents, whereas a relatively fast rate was obtained in less polar solvents. In addition, the TTF groups of the allene also accelerate the racemization rate. These results suggest that the racemization mechanism occurs via a non-polar diradical structure.

  16. Influence of racemic higenamine on the sinus node

    OpenAIRE

    Yu, Fengxia; KONG, LINGTING; Wang, Shujuan

    2012-01-01

    The aim of this study was to explore the mechanism of racemic higenamine in the treatment of sick sinus syndrome (SSS). A total of 40 New Zealand rabbits were randomly divided into normal sinus node and damaged sinus node (SND) groups, and each group was randomly divided into treatment and control groups (n=10). The SND model was established by formaldehyde wet dressing of the sinus node area. The treatment groups were administered an intravenous infusion of 0.04 mg/kg racemic higenamine via ...

  17. Abiotic racemization kinetics of amino acids in marine sediments

    DEFF Research Database (Denmark)

    Steen, Andrew; Jørgensen, Bo Barker; Lomstein, Bente Aagaard

    2013-01-01

    Enantiomeric ratios of amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic racemize abiotically. Based on a heating experiment, we report Arrhenius parameters...... between different amino acids or depths. These results can be used in conjunction with measurements of sediment age to predict the ratio of D:L amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial...

  18. Abiotic Racemization Kinetics of Amino Acids in Marine Sediments

    OpenAIRE

    Steen, Andrew D.; Bo Barker Jørgensen; Bente Aa Lomstein

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth be...

  19. [Enantioseparation of metalaxyl racemate by simulated moving bed chromatography].

    Science.gov (United States)

    Chen, Tao; Chen, Xiange; Xu, Junye; Fan, Jun; Yu, Ying; Zhang, Weiguang

    2016-01-01

    Due to some advantages such as high precision, high efficiency and low consumption of organic solvents, chromatographic separation technique by simulated moving bed (SMB) has attracted considerable attention in the past decades. Herein, the enantioseparation of metalaxyl racemate on EnantioPak OD columns has been carried out by SMB chromatography with the mixture of hexane-ethanol (70 :30, v/v). The elution order of two metalaxyl enantiomers under current chromatographic conditions was determined by HPLC with the optical rotation detector. Then, the influence of running parameters, such as the concentration, flow rate and switch time on the resolution of metalaxyl racemate has been studied in detail. In addition, the separation results from SMB and the preparative chromatography have been compared under the same concentrations. The results showed that the retention of S-(+)-metalaxyl was weaker than R-(-)-metalaxyl and S-(+)-metalaxyl was eluted first. Most importantly, metalaxyl racemate was well separated by SMB chromatography under linear or non-linear conditions, and the purity of each enantiomer product was over 99%. Furthermore, the amount separated by SMB was much more than by the preparative chromatography with racemate concentration of 15 mg/mL, and the mobile phase consumption was one-ninth of the latter. In brief, these results provide us important information for the future development of large-scale

  20. Practical Tactics in Resolution of Racemates via Diastereomeric Salt Formation

    Institute of Scientific and Technical Information of China (English)

    HE,Xu-Chang; QI,Chuang-Yu

    2007-01-01

    A practical tactics in the classical resolutions was illustrated for affording the desired isomers in maximum yields. According to the practical tactics resolution of racemic ethyl nipecotate, Corey lactone and huperzine A intermediate was successfully practiced. The basis of this practicability is the well-known Marckwald principle.

  1. Abiotic racemization kinetics of amino acids in marine sediments.

    Directory of Open Access Journals (Sweden)

    Andrew D Steen

    Full Text Available The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5-11×10(-5 yr(-1. These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  2. Scalemic and racemic imprinting with a chiral crosslinker.

    Science.gov (United States)

    Hebert, Britney; Meador, Danielle S; Spivak, David A

    2015-08-26

    The development of molecularly imprinted chiral stationary phases has traditionally been limited by the need for a chiral pure template. Paradoxically, availability of a chiral pure template largely defeats the purpose of developing a chiral stationary phase. To solve this paradox, imprinting of scalemic and racemic template mixtures was investigated using both chiral (N-α-bismethacryloyl-L-alanine) and achiral (N,O-bisacrylamide ethanolamine) crosslinkers. Imprinting of scalemic mixtures provided polymers capable of partial separation of Boc-tyrosine enantiomers with virtually the same results when using either the chiral or achiral crosslinker. However, the chiral crosslinker was required for chiral differentiation by the racemic imprinted polymers which were evaluated in both batch rebinding and chromatographic modes. Batch rebinding analysis revealed intersecting binding isotherms for the L- and D-Boc-tyrosine, indicating bias for the D or L enantiomer is concentration dependent. Partial chromatographic separation was achieved by the racemic imprinted polymers providing variable D or L bias in equal probability over multiple replicates of polymer synthesis. Correlation of enantiomer bias with the batch rebinding results and optimization of HPLC parameters are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Influence of racemic higenamine on the sinus node.

    Science.gov (United States)

    Yu, Fengxia; Kong, Lingting; Wang, Shujuan

    2013-02-01

    The aim of this study was to explore the mechanism of racemic higenamine in the treatment of sick sinus syndrome (SSS). A total of 40 New Zealand rabbits were randomly divided into normal sinus node and damaged sinus node (SND) groups, and each group was randomly divided into treatment and control groups (n=10). The SND model was established by formaldehyde wet dressing of the sinus node area. The treatment groups were administered an intravenous infusion of 0.04 mg/kg racemic higenamine via the marginal ear vein within 5 min. The electrophysiological indicators of sinoatrial function, including the sinus node recovery time (SNRT), corrected sinus node recovery time (CSNRT), total sinoatrial conduction time (TSACT) and sinus cycle length (SCL), were determined before and 20 min after medication and the changes in these indicators were evaluated. The two control groups were administered 10 ml physiological saline. Following the administration of racemic higenamine, the SNRT, CSNRT, TSACT and SCL in the normal sinus node and SND groups were significantly shortened compared with those in the control groups (Pnode group (Pnode was statistically significant (Pnode self-discipline and improvement of sinoatrial and atrioventricular conduction function.

  4. Age estimation based on aspartic acid racemization in human sclera.

    Science.gov (United States)

    Klumb, Karolin; Matzenauer, Christian; Reckert, Alexandra; Lehmann, Klaus; Ritz-Timme, Stefanie

    2016-01-01

    Age estimation based on racemization of aspartic acid residues (AAR) in permanent proteins has been established in forensic medicine for years. While dentine is the tissue of choice for this molecular method of age estimation, teeth are not always available which leads to the need to identify other suitable tissues. We examined the suitability of total tissue samples of human sclera for the estimation of age at death. Sixty-five samples of scleral tissue were analyzed. The samples were hydrolyzed and after derivatization, the extent of aspartic acid racemization was determined by gas chromatography. The degree of AAR increased with age. In samples from younger individuals, the correlation of age and D-aspartic acid content was closer than in samples from older individuals. The age-dependent racemization in total tissue samples proves that permanent or at least long-living proteins are present in scleral tissue. The correlation of AAR in human sclera and age at death is close enough to serve as basis for age estimation. However, the precision of age estimation by this method is lower than that of age estimation based on the analysis of dentine which is due to molecular inhomogeneities of total tissue samples of sclera. Nevertheless, the approach may serve as a valuable alternative or addition in exceptional cases.

  5. Apical pattern of fruit production in the racemes of Ceratonia siliqua (Leguminosae: Caesalpinioideae): role of pollinators.

    Science.gov (United States)

    Arista, M; Ortiz, P L; Talavera, S

    1999-12-01

    Fruit production and arrangement within the raceme were studied in two dioecious populations of Ceratonia siliqua (Leguminosae: Caesalpinioideae), an arboreal species that produces caulogenous racemes (emerging only from the old branches) with numerous flowers. Fruit production per raceme was low and similar between years and populations and even between individuals. During flowering, there were considerable flower losses from predation and lack of pollination. A mean of nine flowers per raceme began the transformation into fruits, of which 77% aborted. The final fruit production per raceme increased significantly following hand pollination, but was always very much lower than the availability of flowers in the raceme. The results suggest that fruit production of each raceme is limited by both availability of resources and a deficient pollination. In racemes setting fruit arrangement follows a definite pattern that remains constant between years and populations: fruit production was significantly higher in the apical zone of the raceme and lower in the basal zone. The pollinators of C. siliqua (flies and wasps) showed a clear preference for beginning their visits at the apex of a raceme. As a result, the pollen load deposited on the stigmas decreased from apex to base of the raceme. In most of the flowers situated in the central and basal zone of the raceme, the number of pollen grains deposited on their stigmas was lower than the number of their ovules. The high number of seeds in developed fruits suggests that the plant selectively aborts flowers that receive a smaller pollen load. The results indicate that the final pattern of fruit arrangement within the raceme is a direct result of pollinator activity.

  6. Ionothermal Synthesis and Phase Transformation of Organic-inorganic Hybrid Neutral Zincophosphate Cluster[Zn(HPO4)(H2PO4)][C6H10N3O2

    Institute of Scientific and Technical Information of China (English)

    DONG Zhao-jun; YAN Yan; ZHENG Rong-feng; LIU Dan; LI Ji-yang; HAN Zhen-guo; YU Ji-hong

    2011-01-01

    Ionothermal synthesis was used to prepare a novel amino acid containing hybrid zincophosphate monomer,[Zn(HPO4)(H2PO4)][C6H10N3O2](denoted as ZnPO-CJ58).The inorganic framework of[Zn(HPO4)(H2PO4)]·[C6H10N3O2]consists of 4-membered rings formed by ZnO3OH is and PO2(OH)2 tetrahedra.The HPO4 and amino acid moieties hang on the Zn center.Such a framework is stabilized by extensive multipoint hydrogen bonds involving the phosphate units and histidine molecules to form a pseudo-3D supramolecular structure.It is noteworthy that ZnPO-CJ58 is the first zinc phosphate cluster with amino acid acting as the ligand.It exhibits photoluminescence excited at a wavelength of 220 nm.Interestingly,ZnPO-CJ58 can transform into a layered structure (C6H10N3O2)Zn2·(HPO4)(PO4)·H2O(ZnPO-CJ36) through further reacting with water or zinc acetate dihydrate in water at 85 ℃ for 1 h.This work will be helpful for the synthesis of crystalline inorganic-organic hybrid materials with biofunctional molecules.

  7. Racemization of Valine by Impact-Induced Heating

    Science.gov (United States)

    Furukawa, Yoshihiro; Takase, Atsushi; Sekine, Toshimori; Kakegawa, Takeshi; Kobayashi, Takamichi

    2017-05-01

    Homochirality plays an important role in all living organisms but its origin remains unclear. It also remains unclear whether such chiral molecules survived terrestrial heavy impact events. Impacts of extraterrestrial objects on early oceans were frequent and could have affected the chirality of oceanic amino acids when such amino acids accumulated during impacts. This study investigated the effects of shock-induced heating on enantiomeric change of valine with minerals such as olivine ([Mg0.9, Fe0.1]2SiO4), hematite (Fe2O3), and calcite (CaCO3). With a shock wave generated by an impact at 0.8 km/s, both uc(d)- and uc(l)-enriched valine were significantly decomposed and partially racemized under all experimental conditions. Different minerals had different shock impedances; therefore, they provided different P-T conditions for identical impacts. Furthermore, the high pH of calcite promoted the racemization of valine. The results indicate that in natural hypervelocity impacts, amino acids in shocked oceanic water would have decomposed completely, since impact velocity and the duration of shock compression and heating are typically greater in hypervelocity impact events than those in experiments. Even with the shock wave by the impact of small and decelerated projectiles in which amino acids survive, the shock heating may generate sufficient heat for significant racemization in shocked oceanic water. However, the duration of shock induced heating by small projectiles is limited and the population of such decelerated projectiles would be limited. Therefore, even though impacts of asteroids and meteorites were frequent on the prebiotic Earth, impact events would not have significantly changed the ee of proteinogenic amino acids accumulated in the entire ocean.

  8. Separation and enrichment of enantiopure from racemic compounds using magnetic levitation.

    Science.gov (United States)

    Yang, Xiaochuan; Wong, Shin Yee; Bwambok, David K; Atkinson, Manza B J; Zhang, Xi; Whitesides, George M; Myerson, Allan S

    2014-07-18

    Crystallization of a solution with high enantiomeric excess can generate a mixture of crystals of the desired enantiomer and the racemic compound. Using a mixture of S-/RS-ibuprofen crystals as a model, we demonstrated that magnetic levitation (MagLev) is a useful technique for analysis, separation and enantioenrichment of chiral/racemic products.

  9. Enantioseparation of Racemic Naproxen Esters on Cellulose Tris (4-methylbenzoate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Several kinds of racemic naproxen ester were successfully separated on CTMB chiral stationary phase with hexane-ethanol (98:2, vol./vol.) as the mobile phase. The influence of mobile phase composition and structure of racemic naproxen ester on chiral separation was studied and the chiral recognition mechanism of CTMB was discussed.

  10. Enantioseparation of Racemic Naproxen Esters on Cellulose Tris(4—methylbenzoate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    BaoHaiSHAO; XiuZhuXU; 等

    2002-01-01

    Several kinds of racemic naproxen ester were successfully separated on CTMB chiral stationary phase with hexane-ethanol(98:2,vol./vol.) as the mobile phase. The influence of mobile phase composition and structure of racemic naproxen ester on chiral separation was studied and the chiral recognition mechanism of CTMB was discussed.

  11. Meso- and racemic-DMSA as Antidotes in Heavy Metal Poisoning

    Science.gov (United States)

    2001-09-01

    UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADP013383 TITLE: Meso- and racemic-DMSA as Antidotes in Heavy Metal Poisoning...comprise the compilation report: ADP013371 thru ADP013468 UNCLASSIFIED 13. Meso- AND racemic-DMSA AS ANTIDOTES IN HEAVY METAL POISONING 1Maja Blanu~a

  12. Support influences in the Pd-catalyzed racemization and dynamic kinetic resolution of chiral benzylic amines

    NARCIS (Netherlands)

    Parvulescu, A.N.; Jacobs, P.A.; De Vos, D.E.

    2009-01-01

    The acid–base properties of the supports for Pd catalysts strongly affect their performance in racemization and dynamic kinetic resolution (DKR) of chiral benzylic amines. The need for a basic support was proven by comparing the racemization results obtained for Pd on silica, on LDH (layered double

  13. Aspartic Acid Racemization and Age-Depth Relationships for Organic Carbon in Siberian Permafrost

    Science.gov (United States)

    Brinton, Karen L. F.; Tsapin, Alexandre I.; Gilichinsky, David; McDonald, Gene D.

    2002-03-01

    We have analyzed the degree of racemization of aspartic acid in permafrost samples from Northern Siberia, an area from which microorganisms of apparent ages up to a few million years have previously been isolated and cultured. We find that the extent of aspartic acid racemization in permafrost cores increases very slowly up to an age of ~25,000 years (around 5 m in depth). The apparent temperature of racemization over the age range of 0-25,000 years, determined using measured aspartic acid racemization rate constants, is -19°C. This apparent racemization temperature is significantly lower than the measured environmental temperature (-11 to -13°C) and suggests active recycling of D-aspartic acid in Siberian permafrost up to an age of around 25,000 years. This indicates that permafrost organisms are capable of repairing some molecular damage incurred while in a "dormant" state over geologic time.

  14. Chiral separation of racemic drugs using molecular imprinting

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Molecularly imprinted polymers (MIPs) of (S)-ketoprofen and (S)-naproxen are prepared using non-covalent imprinting in the presence of template molecules. The prepared MIPs are used as the chiral stationary phase to separate ramemic naproxen and ketoprofen. The results show that racemic naproxen and ketoprofen are efficiently resolved on MIPs. The effect of concentration of acetic acid in the mobile phase is studied, and the data are analyzed using the affinity chromatography model, and the close agreement is achieved between the simulated and experimental curves. The results suggest that the affinity chromatography mechanism controls the retention in this system. Moreover, the affinity chromatography equilibrium constants on (S)-naproxen and (S)-ketoprofen are estimated.

  15. Racemization of enantiopure secondary alcohols by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase.

    Science.gov (United States)

    Musa, Musa M; Phillips, Robert S; Laivenieks, Maris; Vieille, Claire; Takahashi, Masateru; Hamdan, Samir M

    2013-05-07

    Controlled racemization of enantiopure phenyl-ring-containing secondary alcohols is achieved in this study using W110A secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus (W110A TeSADH) and in the presence of the reduced and oxidized forms of its cofactor nicotinamide-adenine dinucleotide. Racemization of both enantiomers of alcohols accepted by W110A TeSADH, not only with low, but also with reasonably high, enantiomeric discrimination is achieved by this method. Furthermore, the high tolerance of TeSADH to organic solvents allows TeSADH-catalyzed racemization to be conducted in media containing up to 50% (v/v) of organic solvents.

  16. N-heterocyclic carbene-ruthenium complexes for the racemization of chiral alcohols.

    Science.gov (United States)

    Bosson, Johann; Nolan, Steven P

    2010-03-19

    The activity of well-defined 16-electron ruthenium complexes bearing an N-heterocyclic carbene ligand in the racemization of chiral alcohols is reported. Mechanistic considerations are also presented.

  17. Covalent anchoring of a racemization catalyst to CALB-beads: towards dual immobilization of DKR catalysts

    NARCIS (Netherlands)

    Wieczorek, B.; Träff, A.; Krumlinde, P.; Dijkstra, H.P.; Egmond, M.R.; van Koten, G.; Bäckvall, J.-E.; Klein Gebbink, R.J.M.

    2011-01-01

    The preparation of a heterogeneous bifunctional catalytic system, combining the catalytic properties of an organometallic catalyst (racemization) with those of an enzyme (enantioselective acylation) is described. A novel ruthenium phosphonate inhibitor was synthesized and covalently anchored to a

  18. Narcolepsy Treated with Racemic Amphetamine during Pregnancy and Breastfeeding.

    Science.gov (United States)

    Öhman, Inger; Wikner, Birgitta Norstedt; Beck, Olof; Sarman, Ihsan

    2015-08-01

    This case report describes a woman with narcolepsy treated with racemic amphetamine (rac-amphetamine) during pregnancy and breastfeeding with follow-up on the infant's development up to 10 months of age. The pregnancy outcome and the pharmacokinetics of rac-amphetamine were studied during breastfeeding. The pregnancy and the delivery were uneventful. Concentrations of rac-amphetamine were determined in the plasma of the mother and infant, and in the breast milk with a liquid chromatography-mass spectrometry method. Samples were obtained at 2, 5, and 9 weeks postpartum. The transfer of rac-amphetamine to the breast milk was extensive (mean milk/maternal plasma concentration ratio approximately 3). The breastfed infant had a low plasma concentration of rac-amphetamine (about 9% of the maternal plasma level) and the calculated relative infant dose was low (2%). No adverse effects were observed in the breastfed infant. The infant's somatic and psychomotor development up to 10 months of age was normal. Further studies of amphetamine prescribed for medical reasons during pregnancy and lactation are needed.

  19. Non-racemic mixture model: a computational approach.

    Science.gov (United States)

    Polanco, Carlos; Buhse, Thomas

    2017-01-01

    The behavior of a slight chiral bias in favor of l-amino acids over d-amino acids was studied in an evolutionary mathematical model generating mixed chiral peptide hexamers. The simulations aimed to reproduce a very generalized prebiotic scenario involving a specified couple of amino acid enantiomers and a possible asymmetric amplification through autocatalytic peptide self-replication while forming small multimers of a defined length. Our simplified model allowed the observation of a small ascending but not conclusive tendency in the l-amino acid over the d-amino acid profile for the resulting mixed chiral hexamers in computer simulations of 100 peptide generations. This simulation was carried out by changing the chiral bias from 1% to 3%, in three stages of 15, 50 and 100 generations to observe any alteration that could mean a drastic change in behavior. So far, our simulations lead to the assumption that under the exposure of very slight non-racemic conditions, a significant bias between l- and d-amino acids, as present in our biosphere, was unlikely generated under prebiotic conditions if autocatalytic peptide self-replication was the main or the only driving force of chiral auto-amplification.

  20. THE CONCEPT OF RACEMATES AND THE SOAI-REACTION(Isolab'05 Proceedings)

    OpenAIRE

    Luciano, Caglioti; Csongor, Hajdu; Orsolya, Holczknecht; Laszlo, Zekany; Claudia, Zucchi; Karoly, Micskei; Gyula, Palyi; Department of Chemistry Technology of Biologically Active Compounds, University "La Sapienza" Roma; Department of Inorganic and Analytical Chemistry, University of Debrecen:Department of Chemistry, University of Modena and Reggio Emilia; Department of Inorganic and Analytical Chemistry, University of Debrecen; Department of Chemistry, University of Modena and Reggio Emilia

    2006-01-01

    The traditional concept of racemates means an exactly 1:1 mixture of two enantiomeric molecules. Modern analytical and catalytic/preparative discoveries, first of all the Soai-reaction, make necessary a re-evaluation of this concept. The most important aspect of such a revision is the definition of the amount of an excess of one or of the other enantiomer, originating from statistical fluctuation, which can still be "tolerated" when a substance is defined as racemate. The present paper discus...

  1. Preparative chromatographic resolution of racemates using HPLC and SFC in a pharmaceutical discovery environment.

    Science.gov (United States)

    Miller, Larry; Potter, Matt

    2008-11-01

    The preparative chromatographic resolution of racemates has become a standard approach for the generation of enantiomers in pharmaceutical discovery laboratories. This paper will discuss the use of preparative HPLC and SFC to generate individual enantiomers for discovery activities. Analytical HPLC and SFC method development to rapidly screen chiral stationary phases and solvent combinations will be presented. The usefulness of preparative chromatographic resolution of racemates will be demonstrated through the presentation of numerous non-routine case studies from the laboratories at Amgen.

  2. Are the Crystal Structures of Enantiopure and Racemic Mandelic Acids Determined by Kinetics or Thermodynamics?

    Science.gov (United States)

    Hylton, Rebecca K; Tizzard, Graham J; Threlfall, Terence L; Ellis, Amy L; Coles, Simon J; Seaton, Colin C; Schulze, Eric; Lorenz, Heike; Seidel-Morgenstern, Andreas; Stein, Matthias; Price, Sarah L

    2015-09-02

    Mandelic acids are prototypic chiral molecules where the sensitivity of crystallized forms (enantiopure/racemic compound/polymorphs) to both conditions and substituents provides a new insight into the factors that may allow chiral separation by crystallization. The determination of a significant number of single crystal structures allows the analysis of 13 enantiopure and 30 racemic crystal structures of 21 (F/Cl/Br/CH3/CH3O) substituted mandelic acid derivatives. There are some common phenyl packing motifs between some groups of racemic and enantiopure structures, although they show very different hydrogen-bonding motifs. The computed crystal energy landscape of 3-chloromandelic acid, which has at least two enantiopure and three racemic crystal polymorphs, reveals that there are many more possible structures, some of which are predicted to be thermodynamically more favorable as well as slightly denser than the known forms. Simulations of mandelic acid dimers in isolation, water, and toluene do not differentiate between racemic and enantiopure dimers and also suggest that the phenyl ring interactions play a major role in the crystallization mechanism. The observed crystallization behavior of mandelic acids does not correspond to any simple "crystal engineering rules" as there is a range of thermodynamically feasible structures with no distinction between the enantiopure and racemic forms. Nucleation and crystallization appear to be determined by the kinetics of crystal growth with a statistical bias, but the diversity of the mandelic acid crystallization behavior demonstrates that the factors that influence the kinetics of crystal nucleation and growth are not yet adequately understood.

  3. Excellent amino acid racemization results from Holocene sand dollars

    Science.gov (United States)

    Kosnik, M.; Kaufman, D. S.; Kowalewski, M.; Whitacre, K.

    2015-12-01

    Amino acid racemization (AAR) is widely used as a cost-effective method to date molluscs in time-averaging and taphonomic studies, but it has not been attempted for echinoderms despite their paleobiological importance. Here we demonstrate the feasibility of AAR geochronology in Holocene aged Peronella peronii (Echinodermata: Echinoidea) collected from Sydney Harbour (Australia). Using standard HPLC methods we determined the extent of AAR in 74 Peronella tests and performed replicate analyses on 18 tests. We sampled multiple areas of two individuals and identified the outer edge as a good sampling location. Multiple replicate analyses from the outer edge of 18 tests spanning the observed range of D/Ls yielded median coefficients of variation 0.95) for these four amino acids. The ages of 11 individuals spanning the observed range of D/L values were determined using 14C analyses, and Bayesian model averaging was used to determine the best AAR age model. The averaged age model was mainly composed of time-dependent reaction kinetics models (TDK, 71%) based on phenylalanine (Phe, 94%). Modelled ages ranged from 14 to 5539 yrs, and the median 95% confidence interval for the 74 analysed individuals is ±28% of the modelled age. In comparison, the median 95% confidence interval for the 11 calibrated 14C ages was ±9% of the median age estimate. Overall Peronella yields exceptionally high-quality AAR D/L values and appears to be an excellent substrate for AAR geochronology. This work opens the way for time-averaging and taphonomic studies of echinoderms similar to those in molluscs.

  4. SN2-type ring opening of substituted--tosylaziridines with zinc (II) halides: Control of racemization by quaternary ammonium salt

    Indian Academy of Sciences (India)

    Manas K Ghorai; Deo Prakash Tiwari; Amit Kumar; Kalpataru Das

    2011-11-01

    Quaternary ammonium salt mediated highly regioselective ring opening of aziridines with zinc(II) halides to racemic and non-racemic -halo amines in excellent yield and selectivity is described. The reaction proceeds via an SN2-type pathway and the partial racemization of the starting substrate and the product was effectively controlled by using quaternary ammonium salts to afford the enantioenriched products (er up to 95:5).

  5. Estimation of paleotemperature from racemization of aspartic acid in combination with radiocarbon age

    Science.gov (United States)

    Minami, Masayo; Takeyama, Masami; Mimura, Koichi; Nakamura, Toshio

    2007-06-01

    We tried to estimate paleotemperatures from two chosen fossils by measuring D/L aspartic acid ratios and radiocarbon ages of the XAD-2-treated hydrolysate fractions in the fossils. The D/L aspartic acid ratio was measured with a gas chromatograph and radiocarbon dating was performed using a Tandetron AMS system at Nagoya University. The radiocarbon age of a fossil mammoth molar collected from Bykovsky Peninsula, eastern Siberia, was found to be 35,170 ± 300 BP as an average value for the XAD-treated hydrolysate fractions. The aspartic acid in the mammoth molar showed a little evidence of racemization, which might be due to in vivo racemization during the lifetime and then suggests negligible or no postmortem racemization during burial in permafrost. From four animal bone fossils collected from a shell mound excavated at the Awazu submarine archeological site in Lake Biwa, Shiga, Japan, the racemization-based effective mean temperature was calculated to be 15-16 °C using the D/L aspartic acid ratio of about 0.11 and the 14C age of 4500 BP for the XAD-2-treated hydrolysate fractions in the fossils. The average annual temperature was estimated to be 11-12 °C, which approximates to the temperature that the fossils experienced during burial at the site. Although the application of racemization ratios in fossils as paleotemperature indicators is surrounded with many difficulties, the results obtained in this study suggest its feasibility.

  6. Estimation of paleotemperature from racemization of aspartic acid in combination with radiocarbon age

    Energy Technology Data Exchange (ETDEWEB)

    Minami, Masayo [Center for Chronological Research, Nagoya University, Nagoya 464-8602 (Japan)]. E-mail: minami@nendai.nagoya-u.ac.jp; Takeyama, Masami [Department of Earth and Planetary Sciences, School of Science, Nagoya 464-8602 (Japan); Mimura, Koichi [Graduate School of Environmental Studies, Nagoya University, Nagoya 464-8602 (Japan); Nakamura, Toshio [Center for Chronological Research, Nagoya University, Nagoya 464-8602 (Japan)

    2007-06-15

    We tried to estimate paleotemperatures from two chosen fossils by measuring D/L aspartic acid ratios and radiocarbon ages of the XAD-2-treated hydrolysate fractions in the fossils. The D/L aspartic acid ratio was measured with a gas chromatograph and radiocarbon dating was performed using a Tandetron AMS system at Nagoya University. The radiocarbon age of a fossil mammoth molar collected from Bykovsky Peninsula, eastern Siberia, was found to be 35,170 {+-} 300 BP as an average value for the XAD-treated hydrolysate fractions. The aspartic acid in the mammoth molar showed a little evidence of racemization, which might be due to in vivo racemization during the lifetime and then suggests negligible or no postmortem racemization during burial in permafrost. From four animal bone fossils collected from a shell mound excavated at the Awazu submarine archeological site in Lake Biwa, Shiga, Japan, the racemization-based effective mean temperature was calculated to be 15-16 deg. C using the D/L aspartic acid ratio of about 0.11 and the {sup 14}C age of 4500 BP for the XAD-2-treated hydrolysate fractions in the fossils. The average annual temperature was estimated to be 11-12 deg. C, which approximates to the temperature that the fossils experienced during burial at the site. Although the application of racemization ratios in fossils as paleotemperature indicators is surrounded with many difficulties, the results obtained in this study suggest its feasibility.

  7. Limiting racemization and aspartimide formation in microwave-enhanced Fmoc solid phase peptide synthesis.

    Science.gov (United States)

    Palasek, Stacey A; Cox, Zachary J; Collins, Jonathan M

    2007-03-01

    Microwave energy represents an efficient manner to accelerate both the deprotection and coupling reactions in 9-fluorenylmethyloxycarbonyl (Fmoc) solid phase peptide synthesis (SPPS). Typical SPPS side reactions including racemization and aspartimide formation can occur with microwave energy but can easily be controlled by routine use of optimized methods. Cysteine, histidine, and aspartic acid were susceptible to racemization during microwave SPPS of a model 20mer peptide containing all 20 natural amino acids. Lowering the microwave coupling temperature from 80 degrees C to 50 degrees C limited racemization of histidine and cysteine. Additionally, coupling of both histidine and cysteine can be performed conventionally while the rest of the peptide is synthesized using microwave without any deleterious effect, as racemization during the coupling reaction was limited to the activated ester state of the amino acids up to 80 degrees C. Use of the hindered amine, collidine, in the coupling reaction also minimized formation of D-cysteine. Aspartimide formation and subsequent racemization of aspartic acid was reduced by the addition of HOBt to the deprotection solution and/or use of piperazine in place of piperidine.

  8. Racemization of enantiopure secondary alcohols by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase

    KAUST Repository

    Musa, Musa M.

    2013-01-01

    Controlled racemization of enantiopure phenyl-ring-containing secondary alcohols is achieved in this study using W110A secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus (W110A TeSADH) and in the presence of the reduced and oxidized forms of its cofactor nicotinamide-adenine dinucleotide. Racemization of both enantiomers of alcohols accepted by W110A TeSADH, not only with low, but also with reasonably high, enantiomeric discrimination is achieved by this method. Furthermore, the high tolerance of TeSADH to organic solvents allows TeSADH-catalyzed racemization to be conducted in media containing up to 50% (v/v) of organic solvents. © 2013 The Royal Society of Chemistry.

  9. Comparative Optical Separation of Racemic Ibuprofen by Using Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    Dalkeun; PARK; Joong; Kee; LEE; 等

    2002-01-01

    Ibprofen is widely used as a non-steroidal anti-inflammatory drug and poduced as racemic mixture.Its pharmacological activity resides only is S-(+)-enantiomer,and R-(-)-enantiomer is not only inactive but also has many side effects.Thus it is necessary to separate Renantiomer from racemic ibuprofen.We studied optical separation of racemic Ibuprofen with chiral high performance liquid chromatography(HPLC).,Out of three different chiral stationary phases,which were selected on the basis of structure and availability,two were found to be effective.There was optimum eluent composition for each stationary phase for good resolution in optical separation.Resolution decreased with increase of eluent flow rate,but effect of injection volume on resolution was insignificant at high eluent flow rate.

  10. Emulsification-Induced Homohelicity in Racemic Helical Polymer for Preparing Optically Active Helical Polymer Nanoparticles.

    Science.gov (United States)

    Zhao, Biao; Deng, Jinrui; Deng, Jianping

    2016-04-01

    Optically active nano- and microparticles have constituted a significant category of advanced functional materials. However, constructing optically active particles derived from synthetic helical polymers still remains as a big challenge. In the present study, it is attempted to induce a racemic helical polymer (containing right- and left-handed helices in equal amount) to prefer one predominant helicity in aqueous media by using emulsifier in the presence of chiral additive (emulsification process). Excitingly, the emulsification process promotes the racemic helical polymer to unify the helicity and directly provides optically active nanoparticles constructed by chirally helical polymer. A possible mechanism is proposed to explain the emulsification-induced homohelicity effect. The present study establishes a novel strategy for preparing chirally helical polymer-derived optically active nanoparticles based on racemic helical polymers.

  11. Age estimation in forensic sciences: Application of combined aspartic acid racemization and radiocarbon analysis

    Energy Technology Data Exchange (ETDEWEB)

    Alkass, K; Buchholz, B A; Ohtani, S; Yamamoto, T; Druid, H; Spalding, S L

    2009-11-02

    Age determination of unknown human bodies is important in the setting of a crime investigation or a mass disaster, since the age at death, birth date and year of death, as well as gender, can guide investigators to the correct identity among a large number of possible matches. Traditional morphological methods used by anthropologists to determine age are often imprecise, whereas chemical analysis of tooth dentin, such as aspartic acid racemization has shown reproducible and more precise results. In this paper we analyze teeth from Swedish individuals using both aspartic acid racemization and radiocarbon methodologies. The rationale behind using radiocarbon analysis is that above-ground testing of nuclear weapons during the cold war (1955-1963) caused an extreme increase in global levels of carbon-14 ({sup 14}C) which have been carefully recorded over time. Forty-four teeth from 41 individuals were analyzed using aspartic acid racemization analysis of tooth crown dentin or radiocarbon analysis of enamel and ten of these were split and subjected to both radiocarbon and racemization analysis. Combined analysis showed that the two methods correlated well (R2=0.66, p < 0.05). Radiocarbon analysis showed an excellent precision with an overall absolute error of 0.6 {+-} 04 years. Aspartic acid racemization also showed a good precision with an overall absolute error of 5.4 {+-} 4.2 years. Whereas radiocarbon analysis gives an estimated year of birth, racemization analysis indicates the chronological age of the individual at the time of death. We show how these methods in combination can also assist in the estimation of date of death of an unidentified victim. This strategy can be of significant assistance in forensic casework involving dead victim identification.

  12. Characteristics of chiral and racemic ketoprofen drugs using terahertz time-domain spectroscopy

    Science.gov (United States)

    Du, Yong; Liu, Jianjun; Hong, Zhi

    2013-08-01

    Absorption spectra of chiral S-(+)- and racemic RS-ketoprofen pharmaceutical molecules in crystalline form were recorded in the terahertz region between 6 and 66 cm-1 (0.2 ~ 2.0 THz) by using time-domain terahertz spectroscopic (THz-TDS) measurement. Different distinctive absorption features were observed which are strikingly sensitive to the change of subtle conformational structures within such isostructural crystal molecules. The results suggest that the THz-TDS technique can be definitely used for distinguishing between chiral and racemic compounds in pharmaceutical and biological fields.

  13. Kinetics of Amino Acid racemization (epimerisation) in the dentine of fossil and modern bear teeth

    OpenAIRE

    Torres Pérez-Hidalgo, Trinidad José de

    2003-01-01

    The present study examines the question of whether heating experiments on modern bear teeth dentine model the pattern of D/L racemization in fossil teeth. Using samples of modern bear teeth dentine heated at 65°C, 85°C (up to 53 days), and 105°C (up to 71 days), and three independently dated fossil bear teeth, we have compared the modes of racemization induced by temperature in the modern samples and by time on the fossil samples. We have studied seven amino acids (aspartic and...

  14. Impact of substituents on the enantioseparation of racemic 2-amidotetralins on polysaccharide stationary phases .1. Chiralcel OD

    NARCIS (Netherlands)

    Selditz, U; Copinga, S; Franke, JP; Wikstrom, H; deZeeuw, RA

    1996-01-01

    The direct enantiomeric separation of 32 racemic 2-amidotetralins on the commercially available tris-(3,5-dimethylphenylcarbamate) derivative of cellulose, coated on silica gel (Chiralcel OD), is presented. To date, the selection of a column for the chiral separation of a racemic mixture is done emp

  15. X-ray Structure of Native Scorpion Toxin BmBKTx1 by Racemic Protein Crystallography Using Direct Methods

    Energy Technology Data Exchange (ETDEWEB)

    Mandal, Kalyaneswar; Pentelute, Brad L.; Tereshko, Valentina; Kossiakoff, Anthony A.; Kent, Stephen B.H.; (UC)

    2009-04-08

    Racemic protein crystallography, enabled by total chemical synthesis, has allowed us to determine the X-ray structure of native scorpion toxin BmBKTx1; direct methods were used for phase determination. This is the first example of a protein racemate that crystallized in space group I41/a.

  16. Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Xiao Wu

    2016-01-01

    Full Text Available The catalytic synthesis of cyclic carbonates using carbon dioxide as a C1-building block is a highly active area of research. Here, we review the catalytic production of enantiomerically enriched cyclic carbonates via kinetic resolution of racemic epoxides catalysed by metal-containing catalyst systems.

  17. Kinetic resolution of racemic carboxylic acids through asymmetric protolactonization promoted by chiral phosphonous acid diester.

    Science.gov (United States)

    Sakuma, Masayuki; Sakakura, Akira; Ishihara, Kazuaki

    2013-06-07

    Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.

  18. Sequential micellar electrokinetic chromatography analysis of racemization reaction of alanine enantiomers.

    Science.gov (United States)

    Fu, Rao; Liu, Lina; Guo, Yingna; Guo, Liping; Yang, Li

    2014-02-28

    A novel method for online monitoring racemization reaction of alanine (Ala) enantiomers was developed, by combining sequential sample injection and micellar electrokinetic chromatography (MEKC) technique. Various conditions were investigated to optimize the sequential injection, Ala derivatization and MEKC chiral separation of d-/l-Ala. High reproducibility of the sequential MEKC analysis was demonstrated by analyzing the standard Ala samples, with relative standard deviation values (n=20) of 1.35%, 1.98%, and 1.09% for peak height, peak area and migration time, respectively. Ala racemization was automatically monitored every 40s from the beginning to the end of the reaction, by simultaneous detection of the consumption of the substrate enantiomer and the formation of the product enantiomer. The Michaelis constants of the racemization reaction were obtained by the sequential MEKC method, and were in good agreement with those obtained by traditional off-line enzyme assay. Our study indicated that the present sequential MEKC method can perform fast, efficient, accurate and reproducible analysis of racemization reaction of amino acids, which is of great importance for the determination of the activity of racemase and thus understanding its metabolic functions.

  19. Cooperative catalysis by palladium and a chiral phosphoric acid: enantioselective amination of racemic allylic alcohols.

    Science.gov (United States)

    Banerjee, Debasis; Junge, Kathrin; Beller, Matthias

    2014-11-24

    Cooperative catalysis by [Pd(dba)2] and the chiral phosphoric acid BA1 in combination with the phosphoramidite ligand L8 enabled the efficient enantioselective amination of racemic allylic alcohols with a variety of functionalized amines. This catalytic protocol is highly regio- and stereoselective (up to e.r. 96:4) and furnishes valuable chiral amines in almost quantitative yield.

  20. Parallel Kinetic Resolution of Racemic Aldehydes by Use of Asymmetric Horner-Wadsworth-Emmons Reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Jensen, Jakob Feldthusen; Humble, Rikke Eva

    2000-01-01

    A racemic aldehyde can undergo parallel kinetic resolution (PKR) by simultaneous reaction with two different chiral phosphonates, differing either in the structure of the chiral auxiliary or in the structure of the phosphoryl group (i.e., one (E)- and one (Z)-selective reagent). This strategy all...

  1. Racemization of undesired enantiomers: Immobilization of mandelate racemase and application in a fixed bed reactor.

    Science.gov (United States)

    Wrzosek, Katarzyna; Rivera, Mariel A García; Bettenbrock, Katja; Seidel-Morgenstern, Andreas

    2016-03-01

    Production of optically pure products can be based on simple unselective synthesis of racemic mixtures combined with a subsequent separation of the enantiomers; however, this approach suffers from a 50% yield limitation which can be overcome by racemization of the undesired enantiomer and recycling. Application of biocatalyst for the racemization steps offers an attractive option for high-yield manufacturing of commercially valuable compounds. Our work focuses on exploiting the potential of racemization with immobilized mandelate racemase. Immobilization of crude mandelate racemase via covalent attachment was optimized for two supports: Eupergit(®) CM and CNBr-activated Sepharose 4 Fast Flow. To allow coupling of enzymatic reaction with enantioselective chromatography, a mobile phase composition compatible with both processes was used in enzymatic reactor. Kinetic parameters obtained analyzing experiments carried out in a batch reactor could be successfully used to predict fixed-bed reactor performance. The applicability of the immobilized enzyme and the determined kinetic parameters were validated in transient experiments recording responses to pulse injections of R-mandelic acid. The approach investigated can be used for futher design and optimization of high yield combined resolution processes. The characterized fixed-bed enzymatic reactor can be integrated e.g. with chromatographic single- or multicolumn steps in various configurations.

  2. (-)/(+)-Sparteine induced chirally-active carbon nanoparticles for enantioselective separation of racemic mixtures.

    Science.gov (United States)

    Vulugundam, Gururaja; Misra, Santosh K; Ostadhossein, Fatemeh; Schwartz-Duval, Aaron S; Daza, Enrique A; Pan, Dipanjan

    2016-06-14

    Chiral carbon nanoparticles (CCNPs) were developed by surface passivation using the chiral ligand (-)-sparteine or (+)-sparteine (denoted (-)-SP/CNP and (+)-SP/CNP, respectively). The chirality of the prepared CCNPs was demonstrated by circular dichroism and polarimetry and employed as an enantioselective separation platform for representative racemic mixtures.

  3. An Efficient Method for Racemization of (S)-3-Carbamoylmethyl-5-methylhexanoic Acid

    Institute of Scientific and Technical Information of China (English)

    WU,Ting; GAO,Man; YE,Bo; SHEN,Yongjia

    2009-01-01

    (S)-3-Carbamoylmethyl-5-methylhexanoic acid was heated in xylene and converted into 4-isobutyl-piperidine- 2,6-dione, which was hydrolyzed in aqueous solution of sodium hydroxide to afford the racemate. Our process is much advantageous over the traditional one, with not only less time (ca. 20 h) but also higher yield (76.4%).

  4. Racemization of aspartic acid and phenylalanine in the sweetener aspartame at 100 degrees C.

    Science.gov (United States)

    Boehm, M F; Bada, J L

    1984-01-01

    The racemization half-lives (i.e., the time required to reach a D/L = 0.33) at pH 6.8 for aspartic acid and phenylalanine in the sweetener aspartame (L-aspartyl-L-phenylalanine methyl ester) were determined to be 13 and 23 hours, respectively, at 100 degrees C. Racemization at this pH does not occur in aspartame but rather in its diketopiperazine decomposition product. Our results indicate that the use of aspartame to sweeten neutral pH foods and beverages that are then heated at elevated temperature could generate D-aspartic acid and D-phenylalanine. The nutritive consequences of these D-amino acids in the human diet are not well established, and thus aspartame should probably not be used as a sweetener when the exposure of neutral pH foods and beverages to elevated temperatures is required. At pH 4, a typical pH of most foods and beverages that might be sweetened with aspartame, the half-lives are 47 hours for aspartic acid and 1200 hours for phenylalanine at 100 degrees C. Racemization at pH 4 takes place in aspartame itself. Although the racemization rates at pH 4 are slow and no appreciable racemization of aspartic acid and phenylalanine should occur during the normal use of aspartame, some food and beverage components could conceivably act as catalysts. Additional studies are required to evaluate whether the use of aspartame as a sugar substitute might not in turn result in an increased human consumption of D-aspartic acid and D-phenylalanine. PMID:6591191

  5. Phase-Modulated Nonresonant Laser Pulses Can Selectively Convert Enantiomers in a Racemic Mixture

    DEFF Research Database (Denmark)

    Thomas, Esben Folger; Henriksen, Niels Engholm

    2017-01-01

    Deracemization occurs when a racemic molecular mixture is transformed into a mixture containing an excess of a single enantiomer. Recent advances in ultrafast laser technology hint at the possibility of using shaped pulses to generate deracemization via selective enantiomeric conversion; however......-modulated, nonresonant, linearly polarized Gaussian laser pulses that can selectively deracemize a racemic mixture of 3D-oriented, 3,5-difluoro-3',5'-dibromobiphenyl (F2H3C6-C6H3Br2) molecules, the laser-induced dynamics of which are well studied experimentally. These results strongly suggest that designing a closed......-loop coherent control scheme based on this methodology may lead to the first-ever achievement of enantiomeric conversion via coherent laser light in a laboratory setting....

  6. Amino acid racemization in amber-entombed insects: implications for DNA preservation

    Science.gov (United States)

    Bada, J. L.; Wang, X. S.; Poinar, H. N.; Paabo, S.; Poinar, G. O.

    1994-01-01

    DNA depurination and amino acid racemization take place at similar rates in aqueous solution at neutral pH. This relationship suggests that amino acid racemization may be useful in accessing the extent of DNA chain breakage in ancient biological remains. To test this suggestion, we have investigated the amino acids in insects entombed in fossilized tree resins ranging in age from 10(4). These results suggest that in amber insect inclusions DNA depurination rates would also likely be retarded in comparison to aqueous solution measurements, and thus DNA fragments containing many hundreds of base pairs should be preserved. This conclusion is consistent with the reported successful retrieval of DNA sequences from amber-entombed organisms.

  7. The effects of racemization rate for age estimation of pink teeth.

    Science.gov (United States)

    Sakuma, Ayaka; Saitoh, Hisako; Ishii, Namiko; Iwase, Hirotaro

    2015-03-01

    Pink teeth is thought to result from the seepage of hemoglobin caused by dental pulp decomposition. We investigated whether racemization can be applied for age estimation in cases of pink teeth where the whole tooth is used. The pink teeth used were three cases and the normal teeth for control were five mandibular canines of known age. Age of the pink teeth was calculated on the basis of regression formula obtained from the five control teeth. Only a slight error was noted between the actual and estimated ages of the pink teeth (R(2) = 0.980, r = 0.990): Cases 1-3 actually aged 23, 53, and 59 years were estimated to be 26, 52, and 60 years. Based on our results of testing pink teeth of known age, we suggest that racemization techniques allow for the age estimation of pink teeth using the same methods for normally colored teeth.

  8. Racemic 4-(4-tert-butylphenyl-2,6-dimethylcyclohex-3-enecarboxylic acid

    Directory of Open Access Journals (Sweden)

    Paul D. Robinson

    2008-03-01

    Full Text Available The chirality of the title compound, C19H26O2, is solely generated by the presence of the double bond in the cyclohexene ring. This compound was synthesized to study the interaction of the two enantiomers in the solid state. The resultant racemate is made up of carboxylic acid RS dimers. Intermolecular O—H...O hydrogen bonds produce centrosymmetric R22(8 rings which dimerize the two chiral enantiomers through their carboxyl groups.

  9. Preparation of (+)-1-Phenylethylamine by Optical Resolution of Racemic 1-Phenylethylamine with a Chiral Biopolymer,Casein

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    1 Results It has been reported that crystalline form racemates can be resoluted by various methods[1],but for optical resolution of liquid form racemates,the method is limited in chromatograph.So chiral compounds cannot be obtained on large scale by such method.In our previous paper,(+)-3-chloro-1,2-propanediol has been obtained by optical resolution of its racemata (liquid) with a chiral biopolymer,casein[2].

  10. Effects of Chirality on the Antifungal Potency of Methylated Succinimides Obtained by Aspergillus fumigatus Biotransformations. Comparison with Racemic Ones

    OpenAIRE

    Susana Zacchino; Agustina Postigo; Maximiliano Sortino

    2013-01-01

    Eighteen (3R) and (3R,4R)-N-phenyl-, N-phenylalkyl and N-arylsuccinimides were prepared with high enantioselectivity by biotransformation of maleimides with A. fumigatus. This environmentally friendly, clean and economical procedure was performed by the whole-cell fungal bioconversion methodology. Their corresponding eighteen racemic succinimides were prepared instead by synthetic methods. Both, the racemic and the chiral succinimides were tested simultaneously by the microbroth dilution meth...

  11. [Chiral HPLC determination of conversion and enantiomeric excess of enzyme catalyzed stereoselective esterification of racemic ibuprofen].

    Science.gov (United States)

    Xie, Y; Liu, H; Chen, J

    1998-01-01

    In the study of enzyme catalyzed kinetic resolution of racemates, it is imperative to assay how the optical yield varies with chemical conversion. In this paper, a method using one-time injection to determine enantiomeric excess and conversion of the stereoselective esterification of racemic ibuprofen with n-butanol catalyzed by lipase was developed with a commercially available HPLC CSP column Regis(S, S) Whelk-01. In the linear range of detector, all peak areas of products and substrates are proportional to their concentrations. Because the total mole concentration remains unchanged (equal to the initial value of ibuprofen) in the reaction process, the conversion could be calculated from the peak areas, provided the ratio of response factors was known. The calibration curves of two ibuprofen enantiomers with racemic ibuprofen as external standard were overlapped, indicating fiR = fiS. By investigating the variation of peak areas of products and substrates against conversion (determined by external standard), the ratio of peak area-concentration response factor of ibuprofen butyl ester to that of unreacted ibuprofen was determined to be 1 through linear regressions, from which the conversion could be directly determined by the self normalization of the peak areas. With a mobile phase of IPA/hexane/HAc/triethylamine (15/85/0.2/0.05, V/V, flow rate 0.4 mL/min), the resolution of ibuprofen enantiomers was sufficient for precise enantiomeric purity determination.

  12. Aspartic acid racemization dating of Holocene brachiopods and bivalves from the southern Brazilian shelf, South Atlantic

    Science.gov (United States)

    Barbour Wood, Susan L.; Krause, Richard A.; Kowalewski, Michał; Wehmiller, John; Simões, Marcello G.

    2006-09-01

    The extent of racemization of aspartic acid (Asp) has been used to estimate the ages of 9 shells of the epifaunal calcitic brachiopod Bouchardia rosea and 9 shells of the infaunal aragonitic bivalve Semele casali. Both taxa were collected concurrently from the same sites at depths of 10 m and 30 m off the coast of Brazil. Asp D/L values show an excellent correlation with radiocarbon age at both sites and for both taxa ( r2Site 9 B. rosea = 0.97, r2Site 1 B. rosea = 0.997, r2Site 9 S. casali = 0.9998, r2Site 1 S. casali = 0.93). The Asp ratios plotted against reservoir-corrected AMS radiocarbon ages over the time span of multiple millennia can thus be used to develop reliable and precise geochronologies not only for aragonitic mollusks (widely used for dating previously), but also for calcitic brachiopods. At each collection site, Bouchardia specimens display consistently higher D/L values than specimens of Semele. Thermal differences between sites are also notable and in agreement with theoretical expectations, as extents of racemization for both taxa are greater at the warmer, shallower site than at the cooler, deeper one. In late Holocene marine settings, concurrent time series of aragonitic and calcitic shells can be assembled using Asp racemization dating, and parallel multi-centennial to multi-millennial records can be developed simultaneously for multiple biomineral systems.

  13. Racemic ofloxacin separation by supported-liquid membrane extraction with two organic phases

    Institute of Scientific and Technical Information of China (English)

    唐课文; 周春山; 蒋新宇

    2003-01-01

    Based on chemical thermodynamic theory, racemic ofloxacin is separatedin chiral systems by hollow fiber liquid-supported membrane technology combining with countercurrently fractional extraction. The two chiral solutions containing L-dibenzoyltartaric acid and D-dibenzoylta- rtaric acid in 1-octanol, flow through the lumen side and the shell side of fibers, respectively. The solution which flows through the lumen side of fibers also contains racemic ofloxacin. The wall of hollow fibers is filled with an aqueous of 0.1 mol/L Na2HPO4/H3PO4 buffer solution of pH = 6.86 containing 2 mmol/L of cetyltrimethyl ammonium bromide for 48 h. The fairly polar ofloxacin can cross the membrane back and forth, but dibenzoyltartaric acids cannot cross it. Fractional chiral extraction theory, mass transfer performance of hollow fiber membrane and enantioselectivity are investigated. Mathematical model of R/S = 0.96e0.03NTU for racemic ofloxacin separation by hollow fiber extraction, is established. The optical purity for ofloxacin enantiomers is up to 90% when 11 hollow fiber membrane modules of 22 cm in length in series are used.

  14. Does aspartic acid racemization constrain the depth limit of the subsurface biosphere?

    Science.gov (United States)

    Onstott, T C; Magnabosco, C; Aubrey, A D; Burton, A S; Dworkin, J P; Elsila, J E; Grunsfeld, S; Cao, B H; Hein, J E; Glavin, D P; Kieft, T L; Silver, B J; Phelps, T J; van Heerden, E; Opperman, D J; Bada, J L

    2014-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of ~89 years for 1 km depth and 27 °C and 1-2 years for 3 km depth and 54 °C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 °C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

  15. Does Aspartic Acid Racemization Constrain the Depth Limit of the Subsurface Biosphere?

    Science.gov (United States)

    Onstott, T C.; Magnabosco, C.; Aubrey, A. D.; Burton, A. S.; Dworkin, J. P.; Elsila, J. E.; Grunsfeld, S.; Cao, B. H.; Hein, J. E.; Glavin, D. P.; hide

    2013-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of approximately 89 years for 1 km depth and 27 C and 1-2 years for 3 km depth and 54 C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

  16. Does Aspartic Acid Racemization Constrain the Depth Limit of the Subsurface Biosphere?

    Science.gov (United States)

    Onstott, T C.; Magnabosco, C.; Aubrey, A. D.; Burton, A. S.; Dworkin, J. P.; Elsila, J. E.; Grunsfeld, S.; Cao, B. H.; Hein, J. E.; Glavin, D. P.; Kieft, T. L.; Silver, B. J.; Phelps, T. J.; Heerden, E. Van; Opperman, D. J.; Bada, J. L.

    2013-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of approximately 89 years for 1 km depth and 27 C and 1-2 years for 3 km depth and 54 C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

  17. Does aspartic acid racemization constrain the depth limit of the subsurface biosphere?

    Energy Technology Data Exchange (ETDEWEB)

    Onstott, T. C. [Princeton University; Aubrey, A.D. [Jet Propulsion Laboratory, Pasadena, CA; Kieft, T L [New Mexico Institute of Mining and Technology; Silver, B J [Jet Propulsion Laboratory, Pasadena, CA; Phelps, Tommy Joe [ORNL; Van Heerden, E. [University of the Free State; Opperman, D. J. [University of the Free State; Bada, J L. [Geosciences Research Division, Scripps Instition of Oceanography, Univesity of California San Diego,

    2014-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of ~89 years for 1 km depth and 27 C and 1 2 years for 3 km depth and 54 C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

  18. Acoustic and thermal anomalies in a liquid-glass transition of racemic S(+)-R(-) ketoprofen

    Science.gov (United States)

    Shibata, Tomohiko; Takayama, Haruki; Kim, Tae Hyun; Kojima, Seiji

    2014-01-01

    Acoustic and thermal properties of pharmaceutical racemic S(+)-R(-) ketoprofen were investigated in wide temperature range including glassy, supercooled liquid and liquid states by Brillouin scattering and temperature modulated DSC. Sound velocity and acoustic attenuation exhibited clear changes at 265 K indicating a liquid-glass transition and showed the typical structural relaxation above Tg. The high value of the fragility index m = 71 was determined by the dispersion of the complex heat capacity. New relaxation map was suggested in combination with previous study of dielectric measurement.

  19. Crystal structure of racemic cis-2-amino-1,2-diphenylethanol (ADE

    Directory of Open Access Journals (Sweden)

    Isao Fujii

    2015-12-01

    Full Text Available In the title racemic compound, C14H15NO, the hydroxy and amino groups form a bent tweezer-like motif towards the phenyl groups. In the crystal, enantiomers aggregate with each other and are linked by O—H...N hydrogen bonds, forming chiral 21-helical columnar structures from C(5 chains along the b-axis direction. Left- and right-handed 21 helices are formed from (1S,2R-2-amino-1,2-diphenylethanol and (1R,2S-2-amino-1,2-diphenylethanol, respectively.

  20. [Pharmacokinetic implications associated to the use of drugs as racemates or pure enantiomers].

    Science.gov (United States)

    Speisky, H; Squella, J A; Nuñez-Vergara, L J

    1995-07-01

    This article critically reviews the recent specialized literature concerning the influence of the stereochemical nature of quiral drugs on the pharmacokinetic processes and its pharmacological implications. Evidence is presented indicating that as a function of the type of enantiomer administered, profound differences in the pharmacokinetic profiles, e.g. absorption, distribution, biotransformation and elimination can occur. As a consequence of the enantioselective nature of the drug-organism interaction, major differences in the therapeutic responses can be envisaged depending on whether the drug is administered as a pure enantiomer or as a racemic mixture.

  1. Synthesis of Novel Unsaturated Alkyl Ethers of Racemic Deoxyisopodophyllotoxin as Cytotoxic Agents

    Institute of Scientific and Technical Information of China (English)

    Ju Hong FENG; Hong Xia DING; Yi XIONG; Yuan Jiang PAN; Yong Min ZHANG; Xiao Jiang HAO; Fran(c)oise GU(E)RITTE; Joachim ST(O)CKIGT; Yu ZHAO

    2006-01-01

    A series of isopentenyl-derived unsaturated alkyl ethers 19-31 of racemic deoxyisopodophyllotoxin were designed and synthesized. For comparison, compound 32 with a benzyl group at the same position was also prepared. The cytotoxicities of the synthetic compounds have been screened for six human tumor cell lines such as KB, BEL-7404, A549, Hela, PC-3 and CNE.The results showed that two of them exhibited significant cytotoxicities with their IC50 values on selected cell lines at μmol/L scale.

  2. Lipases as Tools in the Synthesis of Prodrugs from Racemic 9-(2,3-Dihydroxypropyladenine

    Directory of Open Access Journals (Sweden)

    Marcela Krečmerová

    2012-11-01

    Full Text Available Lipases from Geotrichum candidum 4013 (extracellular lipase and cell-bound lipase were immobilized by adsorption on chitosan beads. The enzyme preparations were tested in the synthesis of ester prodrugs from racemic 9-(2,3-dihydroxypropyladenine in dimethylformamide with different vinyl esters (acetate, butyrate, decanoate, laurate, palmitate. The transesterification activities of these immobilized enzymes were compared with commercially available lipases (lipase from hog pancreas, Aspergillus niger, Candida antarctica, Pseudomonas fluorescens. Lipase from Candida antarctica was found to be the most efficient enzyme regarding chemical yield of the desired products, while transesterification by lipase from Aspergillus niger resulted in lower yields.

  3. X-ray Structure of Snow Flea Antifreeze Protein Determined by Racemic Crystallization of Synthetic Protein Enantiomers

    Energy Technology Data Exchange (ETDEWEB)

    Pentelute, Brad L.; Gates, Zachary P.; Tereshko, Valentina; Dashnau, Jennifer L.; Vanderkooi, Jane M.; Kossiakoff, Anthony A.; Kent, Stephen B.H. (UPENN); (UC)

    2008-08-20

    Chemical protein synthesis and racemic protein crystallization were used to determine the X-ray structure of the snow flea antifreeze protein (sfAFP). Crystal formation from a racemic solution containing equal amounts of the chemically synthesized proteins d-sfAFP and l-sfAFP occurred much more readily than for l-sfAFP alone. More facile crystal formation also occurred from a quasi-racemic mixture of d-sfAFP and l-Se-sfAFP, a chemical protein analogue that contains an additional -SeCH2- moiety at one residue and thus differs slightly from the true enantiomer. Multiple wavelength anomalous dispersion (MAD) phasing from quasi-racemate crystals was then used to determine the X-ray structure of the sfAFP protein molecule. The resulting model was used to solve by molecular replacement the X-ray structure of l-sfAFP to a resolution of 0.98 {angstrom}. The l-sfAFP molecule is made up of six antiparallel left-handed PPII helixes, stacked in two sets of three, to form a compact brick-like structure with one hydrophilic face and one hydrophobic face. This is a novel experimental protein structure and closely resembles a structural model proposed for sfAFP. These results illustrate the utility of total chemical synthesis combined with racemic crystallization and X-ray crystallography for determining the unknown structure of a protein.

  4. Combined oral treatment with racemic and meso-2,3-dimercaptosuccinic acid for removal of mercury in rats

    Energy Technology Data Exchange (ETDEWEB)

    Kostial, K.; Restek-Samarzija, N.; Blanusa, M.; Piasek, M. [Inst. for Medical Research and Occupational Health, Zagreb (Croatia); Mones, M.M. [Vanderbilt Univ., Dept. of Chemistry, Nashville, TN (United States); Singh, P.K. [Ellington Agriculture Center, Tennessee Dept. of Agriculture, Food Residue and Toxicology Lab., Nashville, TN (United States)

    1997-11-01

    Racemic dimercaptosuccinic acid (DMSA) was found more efficient than the meso-isoform in enhancing the removal of mercury in rats. However, racemic-DMSA has recently been found more toxic. The efficiency of combined oral treatment with the two isoforms of DMSA for removal of mercury has now been evaluated. Female albino rats were treated orally for four days with meso- (M) and/or racemic- (R) DMSA (1 mmol/kg each), five days after a single intraperitoneal administration of {sup 203}Hg with 0.5 mg HgCl{sub 2}/kg. The animals were divided into six groups according to the number of treatments with each isomer: control (untreated), 4M, IR+3M, 2R+2M, 3R+1M, and 4R. Whole body, kidney, liver and brain mercury contents were measured nine days after {sup 203}Hg administration. In all treated groups retention in the whole body and kidneys was greatly reduced. The groups treated with racemic-DMSA, regardless of the number of doses, showed a greater removal of mercury than the group treated with meso-DMSA alone (4M). All treatments were less efficient in reducing liver retention, and the brain retention was not affected. It was concluded that even a single application of the more toxic racemic-DMSA during a four-day oral treatment regimen is sufficient to improve the removal by meso-DMSA of mercury from rats. (au). 8 refs.

  5. Aspartic acid racemization rate in narwhal (Monodon monoceros) eye lens nuclei estimated by counting of growth layers in tusks

    DEFF Research Database (Denmark)

    Garde, Eva; Heide-Jørgensen, Mads Peter; Ditlevsen, Susanne

    2012-01-01

    Ages of marine mammals have traditionally been estimated by counting dentinal growth layers in teeth. However, this method is difficult to use on narwhals (Monodon monoceros) because of their special tooth structures. Alternative methods are therefore needed. The aspartic acid racemization (AAR......) technique has been used in age estimation studies of cetaceans, including narwhals. The purpose of this study was to estimate a species-specific racemization rate for narwhals by regressing aspartic acid D/L ratios in eye lens nuclei against growth layer groups in tusks (n=9). Two racemization rates were...... rate and (D/L)0 value be used in future AAR age estimation studies of narwhals, but also recommend the collection of tusks and eyes of narwhals for further improving the (D/L)0 and 2kAsp estimates obtained in this study....

  6. Effects of Chirality on the Antifungal Potency of Methylated Succinimides Obtained by Aspergillus fumigatus Biotransformations. Comparison with Racemic Ones

    Directory of Open Access Journals (Sweden)

    Susana Zacchino

    2013-05-01

    Full Text Available Eighteen (3R and (3R,4R-N-phenyl-, N-phenylalkyl and N-arylsuccinimides were prepared with high enantioselectivity by biotransformation of maleimides with A. fumigatus. This environmentally friendly, clean and economical procedure was performed by the whole-cell fungal bioconversion methodology. Their corresponding eighteen racemic succinimides were prepared instead by synthetic methods. Both, the racemic and the chiral succinimides were tested simultaneously by the microbroth dilution method of CLSI against a panel of human opportunistic pathogenic fungi of clinical importance. Chiral succinimides showed higher antifungal activity than the corresponding racemic ones and the differences in activity were established by statistical methods. The bottlenecks for developing chiral drugs are how to obtain them through a low-cost procedure and with high enantiomeric excess. Results presented here accomplish both these objectives, opening an avenue for the development of asymmetric succinimides as new antifungal drugs for pharmaceutical use.

  7. Crystallization Behavior and Relaxation Dynamics of Supercooled S‑Ketoprofen and the Racemic Mixture along an Isochrone

    DEFF Research Database (Denmark)

    Adrjanowicz, Karolina; Kaminski, Kamil; Paluch, Marian

    2015-01-01

    In this paper, we study crystallization behavior and molecular dynamics in the supercooled liquid state of the pharmaceutically important compound ketoprofen at various thermodynamic conditions. Dielectric relaxation for a racemic mixture was investigated in a wide range of temperatures and press......In this paper, we study crystallization behavior and molecular dynamics in the supercooled liquid state of the pharmaceutically important compound ketoprofen at various thermodynamic conditions. Dielectric relaxation for a racemic mixture was investigated in a wide range of temperatures...... of pure enantiomers and their 50–50 equimolar mixture in the metastable supercooled liquid state. Crystallization kinetic studies revealed that at the same isochronal conditions the behavior of the S-enantiomer and R,S-racemic mixture of ketoprofen is entirely different. This was examined in the context...

  8. Thermodynamics of sublimation, crystal lattice energies, and crystal structures of racemates and enantiomers: (+)- and (+/-)-ibuprofen.

    Science.gov (United States)

    Perlovich, German L; Kurkov, Sergey V; Hansen, Lars Kr; Bauer-Brandl, Annette

    2004-03-01

    Thermodynamic differences between ibuprofen (IBP) racemate and the (+)-enantiomer were studied by X-ray diffraction, thermoanalysis, and crystal energy calculations. The thermodynamic functions of sublimation (as a measure of crystal lattice energy) were obtained by the transpiration method. The sublimation enthalpies (DeltaH(sub)) of (+/-)-IBP and (+)-IBP are 115.8 +/- 0.6 and 107.4 +/- 0.5 kJ. mol(-1), respectively. Using the temperature dependency of the saturated vapor pressure, the relative fractions of enthalpy and entropy of the sublimation process were calculated, and the sublimation process for both the racemate and the enantiomer was found to be enthalpy driven (62%). Two different force fields, Mayo et al. (M) and Gavezzotti (G), were used for comparative analysis of crystal lattice energies. Both force fields revealed that the van der Waals term contributes more to the packing energy in (+)-IBP than in (+/-)-IBP. The hydrogen bonding energy, however, contributes at 29.7 and 32.3% to the total crystal lattice energy in (+)-IBP and (+/-)-IBP (M), respectively. Furthermore, different structure fragments of the IBP molecule were analyzed with respect to their contribution to nonbonded van der Waals interactions. The effect of the C-H distance on the van der Waals term of the crystal lattice energy was also studied.

  9. Microbial turnover times in the deep seabed studied by amino acid racemization modelling.

    Science.gov (United States)

    Braun, Stefan; Mhatre, Snehit S; Jaussi, Marion; Røy, Hans; Kjeldsen, Kasper U; Pearce, Christof; Seidenkrantz, Marit-Solveig; Jørgensen, Bo Barker; Lomstein, Bente Aa

    2017-07-18

    The study of active microbial populations in deep, energy-limited marine sediments has extended our knowledge of the limits of life on Earth. Typically, microbial activity in the deep biosphere is calculated by transport-reaction modelling of pore water solutes or from experimental measurements involving radiotracers. Here we modelled microbial activity from the degree of D:L-aspartic acid racemization in microbial necromass (remains of dead microbial biomass) in sediments up to ten million years old. This recently developed approach (D:L-amino acid modelling) does not require incubation experiments and is highly sensitive in stable, low-activity environments. We applied for the first time newly established constraints on several important input parameters of the D:L-amino acid model, such as a higher aspartic acid racemization rate constant and a lower cell-specific carbon content of sub-seafloor microorganisms. Our model results show that the pool of necromass amino acids is turned over by microbial activity every few thousand years, while the turnover times of vegetative cells are in the order of years to decades. Notably, microbial turnover times in million-year-old sediment from the Peru Margin are up to 100-fold shorter than previous estimates, highlighting the influence of microbial activities on element cycling over geologic time scales.

  10. Metabolic and Pharmacokinetic Differentiation of STX209 and Racemic Baclofen in Humans

    Directory of Open Access Journals (Sweden)

    Raymundo Sanchez-Ponce

    2012-09-01

    Full Text Available STX209 is an exploratory drug comprising the single, active R-enantiomer of baclofen which is in later stage clinical trials for the treatment of fragile x syndrome (FXS and autism spectrum disorders (ASD. New clinical data in this article on the metabolism and pharmacokinetics of the R- and S-enantiomers of baclofen presents scientific evidence for stereoselective metabolism of only S-baclofen to an abundant oxidative deamination metabolite that is sterically resolved as the S-enantiomeric configuration. This metabolite undergoes some further metabolism by glucuronide conjugation. Consequences of this metabolic difference are a lower Cmax and lower early plasma exposure of S-baclofen compared to R-baclofen and marginally lower urinary excretion of S-baclofen after racemic baclofen administration. These differences introduce compound-related exposure variances in humans in which subjects dosed with racemic baclofen are exposed to a prominent metabolite of baclofen whilst subjects dosed with STX209 are not. For potential clinical use, our findings suggest that STX209 has the advantage of being a biologically defined and active enantiomer.

  11. Elimination of racemic and enantioenriched metalaxyl based fungicides under tropical conditions in the field.

    Science.gov (United States)

    Monkiedje, Adolphe; Zuehlke, Sebastian; Maniepi, Saurelle Jacqueline Ngouopiho; Spiteller, Michael

    2007-09-01

    The elimination has been studied of racemic and enantioenriched metalaxyl applied as an emulsifiable concentrate and wettable powder combined with copper in a Cameroonian field site. The kinetics of the degradation/dissipation of metalaxyl and its acid metabolite were investigated using reversed phase HPLC-MS/MS, while the enantiomeric ratios were measured by HPLC-MS/MS using a Chiralcel OD-H HPLC column. Some soil enzymes activities were determined concurrently for 120d. The elimination of racemic metalaxyl was shown to be enantioselective, with the R-enantiomer being degraded more slowly than the S-enantiomer. Dissipation followed approximate square root first-order kinetics (R>0.98) without lag phases. The enantiomers of metalaxyl have different elimination rates, with half-lives ranging from only 0.8 to 1.5 days. After application to soil, the elimination of metalaxyl in the copper containing formulation was slower. The activities of acid phosphatase, alkaline phosphatase, and alkaline glucosidase were monitored throughout the experiments. No significant influence of metalaxyl and copper could be observed on these parameters. The significantly shorter half-life values of all forms of metalaxyl under field conditions, compared to the previously reported laboratory derived ones, may have implications for the plant disease control with these fungicides in tropical rainforest areas.

  12. Enigmatic Isovaline: Investigating the Stability, Racemization, and Formation of a Non-biological Meteoritic Amino Acid

    Science.gov (United States)

    Hudson, Reggie; Moore, Marla; Lewis, Ariel; Dworkin, Jason

    2008-01-01

    Among the Murchison meteoritic amino acids, isovaline stands out as being both nonbiological (non-protein) and having a relatively high abundance. While approximately equal amounts of D- and L-isovaline have been reported in Murchison and other CM meteorites, the molecule's structure appears to prohibit its racemization in aqueous solutions. We recently have investigated the low-temperature solid-phase chemistry of both isovaline and valine with an eye toward each molecule's formation, stability, and possible interconversions of D and L enantiomers. Ion-irradiated isovaline- and valinecontaining ices were examined by IR spectroscopy and highly-sensitive liquid chromatography/time-of-flight mass spectral methods to assess both amino acid destruction and racemization. Samples were studied in the presence and in the absence of water-ice, and the destruction of both isovaline and valine was measured as a function of radiation dose. In addition, we have undertaken experiments to synthesize isovaline, valine, and their amino acid isomers by solid-phase radiation-chemical pathways other than the oft-invoked Strecker process. This presentation will review and summarize some of our recent findings. -- Our work has been supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. Experiments were performed in the Cosmic Ice Laboratory (RLH, MHM, AL) and the Astrobiology Analytical Laboratory (JPD, DPG) at the NASA Goddard Space Flight Center.

  13. Non-racemic amino acids in the Murray and Murchison meteorites.

    Science.gov (United States)

    Pizzarello, S; Cronin, J R

    2000-01-01

    Small (1.0-9.2%) L-enantiomer excesses were found in six alpha-methyl-alpha-amino alkanoic acids from the Murchison (2.8-9.2%) and Murray (1.0-6.0%) carbonaceous chondrites by gas chromatography-mass spectroscopy of their N-trifluoroacetyl or N-pentafluoropropyl isopropyl esters. These amino acids [2-amino-2,3-dimethylpentanoic acid (both diastereomers), isovaline, alpha-methyl norvaline, alpha-methyl valine, and alpha-methyl norleucine] are either unknown or rare in the terrestrial biosphere. Enantiomeric excesses were either not observed in the four alpha-H-alpha-amino alkanoic acids analyzed (alpha-amino-n-butyric acid, norvaline, alanine, and valine) or were attributed to terrestrial contamination. The substantial excess of L-alanine reported by others was not found in the alanine in fractionated extracts of either meteorite. The enantiomeric excesses reported for the alpha-methyl amino acids may be the result of partial photoresolution of racemic mixtures caused by ultraviolet circularly polarized light in the presolar cloud. The alpha-methyl-alpha-amino alkanoic acids could have been significant in the origin of terrestrial homochirality given their resistance to racemization and the possibility for amplification of their enantiomeric excesses suggested by the strong tendency of their polymers to form chiral secondary structure.

  14. Enzymatic resolution of racemic amines in a continuous reactor in organic solvents.

    Science.gov (United States)

    Gutman, A L; Meyer, E; Kalerin, E; Polyak, F; Sterling, J

    1992-10-05

    An enzymatic process has been developed for the continuous production of the pharmaceutically important intermediate (R)-1-aminoindan and of the chiral resolving agent (R)-1-(1-naphthyl)ethylamine. The process consists of the subtilisin catalyzed stereoselective aminolysis of the racemic primary amine with an active ester in organic solvent. The competing nonenzymatic reaction has been suppressed by appropriate choice of solvent and reactant's concentration and by minimizing the time of contact between the amine and the active ester. Subtilisin was immobilized on glass beads and the reaction carried out in a continuous-flow column bioreactor. By using a 450-mL column bioreactor containing 5.7 g of subtilisin immobilized on 570 g of glass beads, 1.6 kg of racemic 1-(1-naphthyl)ethylamine was resolved after 320 h of continuous operation with only a slight loss of the enzymatic activity. During the whole process, the optical purity of the chiral amine eluting from the column was higher than 90%. A facile procedure was developed for separating the unreacted (R)-amine from the (S)-amide and for the recycling of the solvent 3-methyl-3-pentanol and the active ester 2,2,2-trifluoroethyl butyrate.

  15. Origins of hydration differences in homochiral and racemic crystals of aspartic acid.

    Science.gov (United States)

    Juliano, Thomas R; Korter, Timothy M

    2015-02-26

    The propensity for crystalline hydrates of organic molecules to form is related to the strength of the interactions between molecules, including the chiral composition of the molecular solids. Specifically, homochiral versus racemic crystalline samples can exhibit distinct differences in their ability to form energetically stable hydrates. The focus of the current study is a comparison of the crystal structures and intermolecular forces found in solid-state L-aspartic acid, DL-aspartic acid, and L-aspartic acid monohydrate. The absence of experimental evidence for the DL-aspartic acid monohydrate is considered here in terms of the enhanced thermodynamic stability of the DL-aspartic acid anhydrate crystal as compared to the L-aspartic acid anhydrate as revealed through solid-state density functional theory calculations and terahertz spectroscopic measurements. The results indicate that anhydrous DL-aspartic acid is the more stable solid, not due to intermolecular forces alone but also due to the improved conformations of the molecules within the racemic solid. Hemihydrated and monohydrated forms of DL-aspartic acid have been computationally evaluated, and in each case, the hydrates produce destabilized aspartic acid conformations that prevent DL-aspartic acid hydrate formation from occurring.

  16. Use Of Amino Acid Racemization To Investigate The Metabolic Activity Of ?Dormant? Microorganisms In Siberian Permafrost

    Science.gov (United States)

    Tsapin, A.; McDonald, G.

    2002-12-01

    search for extraterrestrial life or its remnants is based on studying the most probable environments in which life (extant or extinct) may be found, and determining the maximum period of time over which such life could be preserved. The terrestrial permafrost, inhabited by cold adapted microbes, can be considered as an extraterrestrial analog environment. The cells and their metabolic end-products in Earth's permafrost can be used in the search for possible ecosystems and potential inhabitants on extraterrestrial cryogenic bodies. The study of microorganisms (or their remnants) that were buried for a few million years in permafrost provides us with a unique opportunity to determine the long-term viability of (micro)organisms. We have analyzed the degree of racemization of aspartic acid in permafrost samples from Northern Siberia (Brinton et al. 2002, Astrobiology 2, 77), an area from which microorganisms of apparent ages up to a few million years have previously been isolated and cultured. We find that the extent of aspartic acid racemization in permafrost cores increases very slowly up to an age of approximately 25,000 years (around 5 m depth). The apparent temperature of racemization over the age range 0-25,000 years, determined using measured aspartic acid racemization rate constants, is ?19 C. This apparent racemization temperature is significantly lower than the measured environmental temperature (?11 to ?13 C), and suggests active recycling of D-aspartic acid in Siberian permafrost up to an age of around 25,000 years. This indicates that permafrost organisms are capable of repairing some molecular damage incurred while they are in a ?dormant? state over geologic time.

  17. Highly Stereoselective Methylene Transfers onto Butanediacetal-Protected Chiral Non-Racemic Sulfinyl Imines Using S-Ylide Technology

    Science.gov (United States)

    Bettigeri, Sampada V.; Pischek, Susanna C.

    2009-01-01

    Reaction of sulfur ylide with chiral non-racemic imine afforded the desired aziridine in excellent yield. Diastereomeric ratios of >95:5 were obtained. Both enantiomeric lines of the butanediacetal-protected chiral non-racemic sulfinyl imines were examined. The sulfur ylides were generated in situ upon thermal decarboxylation of carboxylmethyl betaine functionality. The enantiomeric pairs of D-mannitol with (S)-(-)-2-methyl-2-propane sulfinamide and ascorbic acid with (R)-(-)-2-methyl-2-propane sulfinamide resulted in the highest levels of diastereocontrol when performing aziridination reactions. PMID:19319433

  18. Collagen turnover in normal and degenerate human intervertebral discs as determined by the racemization of aspartic acid

    NARCIS (Netherlands)

    Sivan, S.-S.; Wachtel, E.; Tsitron, E.; Sakkee, N.; Ham, F. van der; Groot, J.de; Roberts, S.; Maroudas, A.

    2008-01-01

    Knowledge of rates of protein turnover is important for a quantitative understanding of tissue synthesis and catabolism. In this work, we have used the racemization of aspartic acid as a marker for the turnover of collagen obtained from healthy and pathological human intervertebral disc matrices. We

  19. Apples as enantiospecific bioreagents in the hydrolysis of racemic esters and oxygenation of alcohols obtained during the process

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available Biotransformation carried out by apples (Malus silvestris resulted in enantiospecific hydrolysis of racemic acetates, the derivatives of secondary aromatic-aliphatic or terpenic alcohols. The alcohols are oxygenated to ketones (reversible reaction. The differences in the rate of the hydrolysis of enantiomeric esters enable isolation of pure, unreacted R-acetates.

  20. Collagen turnover in normal and degenerate human intervertebral discs as determined by the racemization of aspartic acid

    NARCIS (Netherlands)

    Sivan, S.-S.; Wachtel, E.; Tsitron, E.; Sakkee, N.; Ham, F. van der; Groot, J.de; Roberts, S.; Maroudas, A.

    2008-01-01

    Knowledge of rates of protein turnover is important for a quantitative understanding of tissue synthesis and catabolism. In this work, we have used the racemization of aspartic acid as a marker for the turnover of collagen obtained from healthy and pathological human intervertebral disc matrices. We

  1. Planar Mn4O cluster homochiral metal-organic framework for HPLC separation of pharmaceutically important (±)-ibuprofen racemate.

    Science.gov (United States)

    Hailili, Reshalaiti; Wang, Li; Qv, Junzhang; Yao, Ruxin; Zhang, Xian-Ming; Liu, Huwei

    2015-04-20

    A planar tetracoordinated oxygen containing a homochiral metal-organic framework (MOF) has been synthesized and characterized that can be used as a new chiral stationary phase in high-performance liquid chromatography to efficiently separate racemates such as pharmaceutically important (±)-ibuprofen and (±)-1-phenyl-1,2-ethanediol.

  2. Versatile Stereocontrol in Asymmetric Horner-Wadsworth-Emmons Resolution of a Racemic Diphenylphosphoryl-Protected a-Aminoaldehyde

    DEFF Research Database (Denmark)

    Kreuder, Reinhard; Rein, Tobias; Reiser, Oliver

    1997-01-01

    In kinetic resolutions of the racemic aldehyde 1 by reaction with chiral phosphonates of type 2, all of which contain the same chiral auxiliary in the same enantiomeric form, any of the four diastereomers 3a, 3b, 4a or 4b can be obtained as the main product by an appropriate choice of reaction pa...

  3. Enantioselective sorption of the chiral fungicide metalaxyl on soil from non-racemic aqueous solutions: Environmental implications.

    Science.gov (United States)

    Celis, Rafael; Gámiz, Beatriz; Facenda, Gracia; Hermosín, María C

    2015-12-30

    Mechanisms governing the enantioselectivity of the processes that determine the behavior of chiral pollutants in the environment need to be better understood. Understanding these mechanisms should help improve predictions of the hazards and risks chiral compounds can pose to people and the environment. We report the results of batch sorption experiments indicating that the sorption of the chiral fungicide metalaxyl on soil from non-racemic initial solutions was enantioselective. While from a racemic initial solution the two enantiomers of metalaxyl were sorbed on the soil to the same extent, increasing the fraction of R-enantiomer in the initial solution led to enhanced sorption of this enantiomer and to reduced sorption of the S-enantiomer. Considering the shape of the sorption isotherms (S-type) and the sorption behavior of model sorbents, we attributed this effect to molecular interactions between metalaxyl enantiomer species at the sorbed state, where R-R metalaxyl interactions appeared to be more favorable than R-S metalaxyl interactions. We discuss important environmental implications of the proposed mechanism, such as those related to the fact that the biological degradation of metalaxyl is known to be an enantioselective process that can yield non-racemic residues in soils shortly after application of the fungicide as a racemic mixture. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Racemic methyl 3,10-dioxa-2-azatricyclo[6.2.1.02,6]undecane-4- carboxylate

    KAUST Repository

    Moosa, Basem

    2011-04-29

    The structure of the racemic title compound, C10H 15NO4, consists of a tricyclic skeleton comprising a six-membered piperidine ring and five-membered isoxazolidine and tetrahydrofuran rings. The piperidine ring adopts a distorted chair conformation, while the isoxazolidine and tetrahydrofuran rings have envelope conformations.

  5. Oxyma-based phosphates for racemization-free peptide segment couplings.

    Science.gov (United States)

    Mitachi, Katsuhiko; Kurosu, Yuki E; Hazlett, Brandon T; Kurosu, Michio

    2016-03-01

    Glyceroacetonide-Oxyma [(2,2-dimethyl-1,3-dioxolan-4-yl)methyl 2-cyano-2-(hydroxyimino)acetate (1)] displayed remarkable physico-chemical properties as an additive for peptide-forming reactions. Although racemization-free amide-forming reactions have been established for N-urethane-protected α-amino acids with EDCI, 1, and NaHCO3 in water or DMF-water media, amide-forming reactions of N-acyl-protected α-amino acids and segment couplings of oligopeptides still require further development. Diethylphosphoryl-glyceroacetonide-oxyma (DPGOx 3) exhibits relative stability in aprotic solvents and is an effective coupling reagent for N-acyl-protected α-amino acids and oligo peptide segments. The conditions reported here is also effective in lactam-forming reactions. Unlike most of the reported coupling reagents, simple aqueous work-up procedures can remove the reagents and by-products generated in the reactions.

  6. Kinetics of Lipase Catalyzed Enantioselective Esterification of Racemic Ibuprofen in Isooctane

    Institute of Scientific and Technical Information of China (English)

    谢渝春; 刘会洲; 陈家镛

    2000-01-01

    The kinetics of Candida rugosa lipase catalyzed esteritlcation of racemic ibuprofen with n-butanol in isooctane was studied. The kinetic study was carried out with the addition of 0.1% and 2% (by volume) of water for enzyme activation respectively when celite was added into isooctane for enzyme dispersion. The specific initial rate for S-ibuprofen can be fitted with the Ping Pong Bi Bi mechanism with dead-end competitive inhibition by the alcohol. The time courses of the enantioselective esteriflcation of the two ibuprofen enantiomers with different initial substrate concentrations and water contents were simulated with a model in which both effects of enzyme inactivation by long term reaction and reversed hydrolytic reaction under high water content were taken into consideration.

  7. FTIR spectroscopy of synthesized racemic nonacosan-10-ol: a model compound for plant epicuticular waxes

    Science.gov (United States)

    2010-01-01

    As there are no published graphically presented, detailed IR spectra of nonacosan-10-ol (occurring naturally and widely in plant epicuticular waxes of nanotube form), near IR FTIR spectroscopy (fundamentals, overtones and combinations) has been performed on laboratory synthesized racemic nonacosan-10-ol, as a crystalline solid on Mylar and polypropylene substrates. Room temperature, in vacuo data are presented graphically, in full, and show evidence of extensive hydrogen bonding, an orthorhombic perpendicular subcell, a methylene wagging progression, diagnostic of all-trans conformational order, and Fermi resonance. Moderate or stronger anharmonicity is confirmed. Detailed discussion, quantitative in parts, is given of the observed spectral features, especially as to how they inform crystal structure and molecular conformation, and assignments given for some of the features. The results will serve as a reference for future IR studies of the natural epicuticular wax nanotube form of (S)-nonacosan-10-ol. PMID:21886346

  8. Lipase-catalyzed Kinetic Resolution of Racemic 1-Trimethylsilylethanol in Organic Solvent

    Institute of Scientific and Technical Information of China (English)

    吴虹; 宗敏华; 王菊芳; 罗涤衡; 娄文勇

    2004-01-01

    The enantioselective esterification of racemic 1-trimethylsilylethanol with acids catalyzed by lipase in organic solvent was successfully performed. The influence of some factors on the reaction was investigated. Among the four lipases explored, Candlda rugosa lipase (CRL) showed the highest activity and enantioselectivity. Octanoic acid was the best acyl donor among the eleven acids studied and n-hexane was the most suitable medium for the reaction. The optimum shaking rate and temperature were found to be 150 r-rain-i and 20~(3 to 30~C, respectively.The enantiomeric excess of the remaining (S)-(-)-1-trimethylsilylethanol was 93% when substrate conversion was 53% upon incubation of the reaction mixture at 30~C, 150 r-rain-i for 12 h.

  9. Amino acid racemization dating of Upper Pleistocene - Holocene terrestrial gastropods from a Mediterranean region (Murcia, SE Spain)

    Science.gov (United States)

    Garcia-Mayordomo, Julian; Ortiz, Jose E.; Torres, Trinidad; Insua-Arevalo, Juan M.; Martinez-Diaz, Jose J.; Altolaguirre, Yul; Canales-Fernandez, Maria L.; Martin-Banda, Raquel

    2014-05-01

    The amino acid racemization method has become a widely used geochronological tool for dating Quaternary deposits. The method is based on the fact that living organisms contain only L-amino acids which gradually racemize into D-amino acids after death. Thus, the D/L ratio increases with time after death until it is equal to 1, that is, when equilibrium is reached. Gastropod shells are particularly useful for amino acid racemization dating. Because the amino acid racemization method is not a numerical dating method in isolation, it needs to be calibrated, mainly with radiometric dating methods. The racemization process is genus- and temperature-dependent. In this work we present a preliminary analysis that compares the radiometric age estimated from different dating methods of a number of gastropods recovered in localities from Murcia (Southeastern Spain), with the age obtained through the amino acid racemization method. Taking advantage of recent paleoseismological research in the Murcia region (SE Spain), 28 gastropods specimens were collected from different trenches dug in young Quaternary alluvial deposits. The specimens were subsequently classified and then analyzed according to the standards protocols of the Biomolecular Stratigraphy Laboratory (UPM, Madrid School of Mines). The species found were Otala lactea, Iberus gualterianus, Sphincterochila candidissima and Theba pisana. The D/L ratios of aspartic acid, leucine, phenylalanine and glutamic acid were determined, and the corresponding average age of each specimen was calculated introducing the D/L values in the age calculation algorithm of Torres et al. (1997) for gastropods of central and southern Spain. The racemization age for each locality was then compared to the radiometric age of the deposit where the specimens were collected. To this respect, the samples were classified in different groups considering the reliability on the age control method. The most reliable sample consists only on dates obtained

  10. Aspartic acid racemization rate in narwhal (Monodon monoceros eye lens nuclei estimated by counting of growth layers in tusks

    Directory of Open Access Journals (Sweden)

    Eva Garde

    2012-11-01

    Full Text Available Ages of marine mammals have traditionally been estimated by counting dentinal growth layers in teeth. However, this method is difficult to use on narwhals (Monodon monoceros because of their special tooth structures. Alternative methods are therefore needed. The aspartic acid racemization (AAR technique has been used in age estimation studies of cetaceans, including narwhals. The purpose of this study was to estimate a species-specific racemization rate for narwhals by regressing aspartic acid d/l ratios in eye lens nuclei against growth layer groups in tusks (n=9. Two racemization rates were estimated: one by linear regression (r2=0.98 based on the assumption that age was known without error, and one based on a bootstrap study, taking into account the uncertainty in the age estimation (r2 between 0.88 and 0.98. The two estimated 2kAsp values were identical up to two significant figures. The 2k Asp value from the bootstrap study was found to be 0.00229±0.000089 SE, which corresponds to a racemization rate of 0.00114−yr±0.000044 SE. The intercept of 0.0580±0.00185 SE corresponds to twice the (d/l0 value, which is then 0.0290±0.00093 SE. We propose that this species-specific racemization rate and (d/l0 value be used in future AAR age estimation studies of narwhals, but also recommend the collection of tusks and eyes of narwhals for further improving the (d/l0 and 2kAsp estimates obtained in this study.

  11. Racemic epinephrine compared to salbutamol in hospitalized young children with bronchiolitis; a randomized controlled clinical trial [ISRCTN46561076

    Directory of Open Access Journals (Sweden)

    LeBlanc John C

    2005-05-01

    Full Text Available Abstract Background Bronchiolitis is the most common cause of lower respiratory tract illness in infancy, and hospital admission rates appear to be increasing in Canada and the United States. Inhaled beta agonists offer only modest short-term improvement. Trials of racemic epinephrine have shown conflicting results. We sought to determine if administration of racemic epinephrine during hospital stay for bronchiolitis improved respiratory distress, was safe, and shortened length of stay. Methods The study was a randomized, double-blind controlled trial of aerosolized racemic epinephrine compared to salbutamol every one to 4 hours in previously well children aged 6 weeks to ≤ 2 years of age hospitalized with bronchiolitis. The primary outcome was symptom improvement as measured by the Respiratory Distress Assessment Instrument (RDAI; secondary outcomes were length of stay in hospital, adverse events, and report of symptoms by structured parental telephone interview one week after discharge. Results 62 children with a mean age of 6.4 months were enrolled; 80% of children had Respiratory Syncytial Virus (RSV. Racemic epinephrine resulted in significant improvement in wheezing and the total RDAI score on day 2 and over the entire stay (p 0.05. Adverse events were not significantly different in the two arms. At one week post-discharge, over half of parents reported that their child still had a respiratory symptom and 40% had less than normal feeding. Conclusion Racemic epinephrine relieves respiratory distress in hospitalized infants with bronchiolitis and is safe but does not abbreviate hospital stay. Morbidity associated with bronchiolitis as identified by parents persists for at least one week after hospital discharge in most infants.

  12. [From the racemate to the eutomer: (S)-ketamine. Renaissance of a substance?].

    Science.gov (United States)

    Adams, H A; Werner, C

    1997-12-01

    The pharmacological profile of ketamine: Until recently, clinically available ketamine was a racemic mixture containing equal amounts of two enantiomers, (S)- and (R)-ketamine. The pharmacological profile of racemic ketamine is characterized by the so called dissociative anesthetic state and profound sympathomimetic properties. Among the different sites of action, N-methyl-D-aspartate (NMDA)-receptor antagonism is considered to be the most important neuropharmacological mechanism of ketamine. Effects on opiate receptors, monoaminergic and cholinergic transmitters, and local anesthetic effects are obvious as well. Following intravenous administration, a rapid onset of action is seen within 1 min, lasting for about 10 min. The anaesthetic state is terminated due to redistribution, followed by hepatic and renal elimination with a half-life period of 2-3 h. For alternative administration, the intramuscular and oral route is also appropriate. The most important adverse effects are hallucinations and excessive increases in blood pressure and heart rate. These reactions can be attenuated or avoided by combining of ketamine with sedative or hypnotic drugs like midazolam and/or propofol. During controlled ventilation, increases in intracranial pressure are unlikely to occur. The special pharmacological profile of (S)-ketamine: In general, the pharmacological properties of (S)-ketamine are comparable to the racemic compound. On the different sites of action, qualitatively comparable effects were found, but significant quantitative differences also became obvious. When compared with (R)-ketamine and the racmic mixture, the analgesic and anesthetic potency of (S)-ketamine is threefold or twofold higher. Thus, a 50% reduction of dosage is possible to achieve comparable clinical results. Because of the faster elimination of (S)-ketamine, better control of anesthesia will be provided. In summary, the pharmacokinetic improvements of (S)-ketamine are characterized by a reduced drug

  13. Enantiomerically pure (1S,5R) and racemic 3-(1-benzothiophen-2-yl)-8-azoniabicyclo 3.2.1 oct-2-ene acetate

    DEFF Research Database (Denmark)

    Frostrup, B.; Peters, D.; Bond, A. D.

    2012-01-01

    The title compound, C15H16NS+center dot C2H3O2-, has been crystallized as both a pure enantiomer (1S,5R) and a racemate. The racemate crystallizes in the space group Cc, with molecules of opposite handedness related to each other by the action of the c-glide. The enantiomer is essentially...... isostructural with the racemate, except that the glide symmetry is violated by interchange of CH and CH2 groups within the seven-membered ring. The space-group symmetry is reduced to P1 with two molecules in the asymmetric unit. The enantiomer structure shows disorder of the thiophene ring for one...... of the molecules in the asymmetric unit. The major component of the disorder has the thiophene ring in the same position as in the racemate, but generates a higher-energy molecular conformation. The minor disorder component has different intermolecular interactions but retains a more stable molecular conformation....

  14. Aspartic acid racemization in dentin of the third molar for age estimation of the Chaoshan population in South China.

    Science.gov (United States)

    Chen, Shisheng; Lv, Yanyi; Wang, Dian; Yu, Xiaojun

    2016-09-01

    Aspartic acid racemization in teeth has been increasingly used to estimate chronological age with a considerably high accuracy in forensic practice. The Chaoshan population in South China is relatively isolated in geography, and has specific lifestyle and dietary inhibits. It is still unknown whether this method is suitable for this population. The aim of this study was to analyze the relationship between chronological age and the d/l aspartic acid ratio in dentin in the third molar tooth of the Chaoshan population. Fifty-eight non-carious third molar teeth (31 mandibles and 27 maxillae), from 58 living individuals of known age (24 males and 34 females), were retrieved. Dentin was extracted from these teeth. The d- and l-aspartic acids in dentins were separated and detected by high performance liquid chromatography (HPLC). Linear regression was performed between the d/l aspartic acid ratio of dentins and chronological age. Results showed that the correlation coefficient (r) was 0.969, and the mean absolute error (MAE) was 2.19 years, its standard deviation (SD) was ±1.53 years, indicating excellent correlation. There was no significant difference in racemization rates of dentin between sexes (P=0.113, F=2.6), or between mandibles and maxillae (P=0.964, F=0.000). Results indicate that the ratio of the d and l forms of aspartic acid of dentins, in the third molar, is closely correlated with chronological age, special lifestyle do no obviously affect the accuracy of the age estimations by aspartic acid racemization of the dentin in the third molar and that aspartic acid racemization in the third molar dentin can be used as an accurate method to estimate chronological age in the Chaoshan population in South China.

  15. Chiral-phase high-performance liquid chromatography of rotenoid racemates

    Science.gov (United States)

    Abidi, S.L.

    1987-01-01

    The high-performance liquid chromatograhic (HPLC) behavior of parent rotenoids (type I) and the hydroxyl-analogues (type II) on three different chiral stationary phases (CSPs) was studied. Separations of optical isomers were achieved in various degrees depending largely upon the rotenoidal structures and the CSP types employed. Enantiomers of all but elliptone compounds were separable on β-cyclodextrin-bonded silica (CDS). Without exception, the 12a-hydroxyrotenoid antipodes were resolved on Pirkle's phenylglycine-bonded silica (PGS) despite unsuccessful attenmpts to resolve the type I rotenoidal racemates. Conversely, optical resolution of the latter rotenoids was accomplished by using a helical polytriphenylmethylacrylate-coated silica (TPS) column and the observed separation factors (α values) ranged from 1.14 to 1.90. The results from HPLC of type II rotenoids on TPS (α = 1.00–1.63) suggested that variations in E-ring structures had profound influence on the resolution outcome. Conjugated double bonds on the E-ring and the desisopropylation of the five-membered E-ring ot type II rotenoids appeared to be important structural features for chiral recognition involving the TPS substrate. In both reversed-phase (CDS) and normal-pahse (PGS and TPS) HPLC modes, the less polar enantiomers were the 6aβ,12aβ-rotenoids as observed in most cases, though this relationship was reversed in the cases of deguelin and hydroxyelliptone probably due to conformational effects of rotenoidal ring systems.

  16. Isotopic evidence for extraterrestrial non-racemic amino acids in the Murchison meteorite.

    Science.gov (United States)

    Engel, M H; Macko, S A

    1997-09-18

    Many amino acids contain an asymmetric centre, occurring as laevorotatory, L, or dextrorotatory, D, compounds. It is generally assumed that abiotic synthesis of amino acids on the early Earth resulted in racemic mixtures (L- and D-enantiomers in equal abundance). But the origin of life required, owing to conformational constraints, the almost exclusive selection of either L- or D-enantiomers, and the question of why living systems on the Earth consist of L-enantiomers rather than D-enantiomers is unresolved. A substantial fraction of the organic compounds on the early Earth may have been derived from comet and meteorite impacts. It has been reported previously that amino acids in the Murchison meteorite exhibit an excess of L-enantiomers, raising the possibility that a similar excess was present in the initial inventory of organic compounds on the Earth. The stable carbon isotope compositions of individual amino acids in Murchison support an extraterrestrial origin -- rather than a terrestrial overprint of biological amino acids-although reservations have persisted. Here we show that individual amino-acid enantiomers from Murchison are enriched in 15N relative to their terrestrial counterparts, so confirming an extraterrestrial source for an L-enantiomer excess in the Solar System that may predate the origin of life on the Earth.

  17. CHROMATOGRAPHIC SEPARATION OF VERAPAMIL RACEMATE USING A VARICOL CONTINUOUS MULTICOLUMN PROCESS

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    R. F. Perna

    2015-12-01

    Full Text Available Abstract Verapamil is a chiral drug that is marketed in its racemic form, but because of the pharmacological effects due to molecule’s chirality, one of the enantiomers is more potent, and the other exhibits different activities of therapeutic interest. The preparative separation of the verapamil enantiomers was performed using a continuous Varicol unit operated on a scale of 1 g/day. Amylose tris(3,5-dimethylphenylcarbamate functioned as the stationary phase, and n-hexane/isopropanol/ethanol mixtures were used as the mobile phase. Diethylamine was used as the additive. The enantiomeric purities were 93.0% for S-(--verapamil and 92.0% for R-(+-verapamil in the raffinate and extract streams, respectively. The unit provided productivities of 0.18 kg of raffinate per day per kg of adsorbent and 0.20 kg of extract per day per kg of adsorbent when using a feed concentration of 12.5 g L-1.

  18. Analysis of metalaxyl racemate using high performance liquid chromatography coupled with four kinds of detectors.

    Science.gov (United States)

    Chen, Tao; Fan, Jun; Gao, Ruiqi; Wang, Tai; Yu, Ying; Zhang, Weiguang

    2016-10-07

    Chiral stationary phase-high performance liquid chromatography coupled with various detectors has been one of most commonly used methods for analysis and separation of chiral compounds over the past decades. Various detectors exhibit different characteristics in qualitative and quantitative studies under different chromatographic conditions. Herein, a comparative evaluation of HPLC coupled with ultraviolet, optical rotation, refractive index, and evaporative light scattering detectors has been conducted for qualitative and quantitative analyses of metalaxyl racemate. Effects of separation conditions on the peak area ratio between two enantiomers, including sample concentration, column temperature, mobile phase composition, as well as flow rate, have been investigated in detail. In addition, the limits of detection, the limits of quantitation, quantitative range and precision for these two enantiomers by using four detectors have been also studied. As indicated, the chromatographic separation conditions have been slight effects on ultraviolet and refractive index detections and the peak area ratio between two enantiomers remains almost unchanged, but the evaporative light scattering detection has been significantly affected by the above-mentioned chromatographic conditions and the corresponding peak area ratios varied greatly. Moreover, the limits of detection, the limits of quantitation, and the quantitative ranges of two enantiomers with UV detection were remarkably lower by 1-2 magnitudes than the others. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Anti-fouling chemistry of chiral monolayers: enhancing biofilm resistance on racemic surface.

    Science.gov (United States)

    Bandyopadhyay, Debjyoti; Prashar, Deepali; Luk, Yan-Yeung

    2011-05-17

    This work reports the resistance to protein adsorption and bacterial biofilm formation by chiral monolayers of polyol-terminated alkanethiols surrounding micrometer-sized patterns of methyl-terminated alkanethiols on gold films. We discover that patterned surfaces surrounded by chiral polyol monolayers can distinguish different stages of biofilm formation. After inoculation on the surfaces, bacteria first reversibly attached on the chiral polyol monolayers. Over time, the bacteria detached from the polyol surfaces, and attached on the hydrophobic micropatterns to form biofilms. Interestingly, while both enantiomers of gulitol- and mannonamide-terminated monolayer resisted adsorption of proteins (bovine serum albumin, lysozyme, and fibrinogen) and confined biofilms formed on the micropatterns, the monolayers formed by the racemic mixture of either pair of enantiomers exhibited stronger antifouling chemistry against both protein adsorption and biofilm formation than monolayers formed by one enantiomer alone. These results reveal the different chemistries that separate the different stages of biofilm formation, and the stereochemical influence on resisting biofoulings at a molecular-level.

  20. Resolution of Racemic Acids, Esters and Amines by Candida rugosa Lipase in Slightly Hydrated Organic Media

    Directory of Open Access Journals (Sweden)

    Andrés R. Alcántara

    2004-01-01

    Full Text Available Commercial crude lipase from Candida rugosa is widely used as a biocatalyst in the resolution of racemic mixtures and in organic synthesis in slightly hydrated organic solvents. In many cases, reproducible results are not obtained when the same crude lipase is used, but from different suppliers of lots, this being due to the presence of different isoenzymes. The current work addresses this problem and strategies to overcome it. The yeast Candida rugosa ATCC 14380 was cultivated in a minimal culture medium, using different substances as inducers and carbon sources. The percentage of inducer that gave the optimum productivity of extracellular lipases was determined. Lyophilized extracellular enzymes were characterized by SDS-PAGE electrophoresis and isoelectric focusing (IEF. Depending on the nature of the carbon source, different isoenzymes were produced in various proportions. These samples were partially purified by different methodologies, including dialysis, adsorption chromatography and precipitation with ammonium sulfate or organic solvents. These characterizations allowed us to explain the relative catalytic activity of different samples, showing that in biocatalysis enzymes should not be treated simply as a »white magic powder« that can solve all the challenges in organic synthesis. Heptyl oleate synthesis, alcoxycarbonylation of amines and hydrolysis of the ester of ketoprofen are excellent reaction tests for the evaluation of lipase samples as biocatalysts.

  1. Enantioselective pharmacokinetics of ketoprofen in calves after intramuscular administration of a racemic mixture.

    Science.gov (United States)

    Plessers, E; Watteyn, A; Wyns, H; Pardon, B; De Baere, S; De Backer, P; Croubels, S

    2015-08-01

    The pharmacokinetic properties of ketoprofen were determined in 4-week-old calves after intramuscular (i.m.) injection of a racemic mixture at a dose of 3 mg/kg body weight. Due to possible enantioselective disposition kinetics and chiral inversion, the plasma concentrations of the R(-) and S(+) enantiomer were quantified separately, using a stereospecific HPLC-UV assay. A distinct predominance of the S(+) enantiomer was observed, as well as significantly different pharmacokinetic parameters between R(-) and S(+) ketoprofen. More in specific, a greater value for the mean area under the plasma concentration-time curve (AUC(0→∞)) (46.92 ± 7.75 and 11.13 ± 2.18 μg·h/mL for the S(+) and R(-) enantiomer, respectively), a lower apparent clearance (Cl/F) (32.8 ± 5.7 and 139.0 ± 25.1 mL/h·kg for the S(+) and R(-) enantiomer, respectively) and a lower apparent volume of distribution (V(d)/F) (139 ± 14.7 and 496 ± 139.4 mL/kg for the S(+) and R(-) enantiomer, respectively) were calculated for the S(+) enantiomer, indicating enantioselective pharmacokinetics for ketoprofen in calves following i.m. administration.

  2. A novel control of enzymatic enantioselectivity through the racemic temperature influenced by reaction media.

    Science.gov (United States)

    Jin, Xin; Liu, Bokai; Ni, Zhong; Wu, Qi; Lin, Xianfu

    2011-05-06

    The influence of reaction media on the racemic temperature (T(r)) in the lipase-catalyzed resolution of ketoprofen vinyl ester was investigated. An effective approach to the control of the enzymatic enantioselectivity and the prediction of the increasing tendency was developed based on the T(r) influenced by reaction media. The T(r) for the resolution catalyzed by Candida rugosa lipase (CRL) was found at 29 °C in aqueous and S-ketoprofen was obtained predominantly at 40 °C. However, CRL showed R-selectivity at 40 °C in diisopropyl ether because the T(r) was changed to 56 °C. CRL, lipase from AYS Amano(®) and Mucor javanicus lipase were further applied for the investigation of the enzymatic enantioselectivity in dioxane, DIPE, isooctane and their mixed media with water. The effects of the reaction medium on T(r) could be related to the solvent hydrophobicity, the lipase conformational flexibility and the interaction between the enantiomers and the lipase.

  3. Estimation of age at death based on aspartic acid racemization in elastic cartilage of the epiglottis.

    Science.gov (United States)

    Matzenauer, Christian; Reckert, Alexandra; Ritz-Timme, Stefanie

    2014-11-01

    Age estimation based on aspartic acid racemization (AAR) has been applied successfully to various tissues. For routine uses, AAR is analyzed in dentine. For cases in which teeth are unavailable, analyzing AAR in purified elastin has been shown to be an alternative method. The suitability of elastic cartilage from the epiglottis as an elastin source for age estimation based on AAR was tested. A total of 65 tissue samples (cartilage) of epiglottis and 45 samples of elastin purified from the elastic cartilage of epiglottis samples were analyzed. While the D-aspartic acid content of total tissue samples increased with age only slowly, its increase with age in purified elastin samples was similar to that in purified elastin from other tissues. The relationship between the D-aspartic acid content and age was shown to be close enough for age estimation based on AAR in purified elastin from the elastic cartilage of the epiglottis, provided a sufficient quality of elastin purification. Age estimation based on AAR in purified elastin from the epiglottis might serve as a valuable alternative in cases in which other tissues (e.g., teeth) are unavailable.

  4. Racemic salbutamol and levosalbutamol in mild persistent asthma: A comparative study of efficacy and safety

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    Rituparna Maiti

    2011-01-01

    Full Text Available Aim : The effect of monotherapy with racemic salbutamol and levosalbutamol on symptoms, quality of life, and pulmonary function has been assessed and compared in mild persistent asthma. Materials and Methods : A randomized, open, parallel clinical study was conducted on 60 patients of mild persistent asthma. After baseline assessments, salbutamol was prescribed to 30 patients and levosalbutamol to another 30 for 4 weeks. The efficacy variables were change in asthma symptom scoring, pulmonary function test, and Mini Asthma Quality of Life Questionnaire (MiniAQLQ scoring. At follow-up, the patients were re-evaluated and analyzed by statistical tools. Results : Shortness of breath (P<0.001, chest tightness (P=0.033, wheeze (P=0.01, cough (P=0.024, and overall asthma symptom score (P<0.001 were significantly decreased in the levosalbutamol group in comparison to the salbutamol group. Results of MiniAQLQ revealed that improvement in symptoms (P=0.018, activity limitations (P=0.03, environmental stimuli (P=0.013-related scoring and overall MiniAQLQ scoring (P<0.001 was statistically significant in the levosalbutamol group. Percentage reversibility of forced expiratory volume at one second (P=0.034, forced vital capacity (P=0.029, peak expiratory flow rate (P=0.0003 was found to be superior in the levosalbutamol group. Conclusion : Levosalbutamol was found to be superior compared to recemic salbutamol in mild persistent asthma.

  5. Thermodynamic Study of Racemic Ibuprofen Separation by Liquid Chromatography Using Cellulose-Based Stationary Phase

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    Wilson M. Ferrari

    2016-01-01

    Full Text Available Ibuprofen is a nonsteroidal anti-inflammatory drug (NSAID, also known for its significant antipyretic and analgesic properties. This chiral drug is commercialized in racemic form; however, only S-(+-ibuprofen has clinical activities. In this paper the effect of temperature change (from 288.15 to 308.15 K on the ibuprofen resolution was studied. A column (250×4.6 mm packed with tris(3,5-dimethylphenylcarbamate was used to obtain the thermodynamic parameters, such as enthalpy change (ΔH, entropy change (ΔS, variation enthalpy change (ΔΔH, variation entropy change (ΔΔS, and isoenantioselective temperature (Tiso. The mobile phase was a combination of hexane (99%, isopropyl alcohol (1%, and TFA (0.1%, as an additive. The conditions led to a selectivity of 1.20 and resolution of 4.55. The first peak, R-(−-ibuprofen, presented an enthalpy change of 7.21 kJ/mol and entropy change of 42.88 kJ/K·mol; the last peak, S-(+-ibuprofen, has an enthalpy change of 8.76 kJ/mol and 49.40 kJ/K·mol of entropy change.

  6. Age estimation of archaeological remains using amino acid racemization in dental enamel: a comparison of morphological, biochemical, and known ages-at-death.

    Science.gov (United States)

    Griffin, R C; Chamberlain, A T; Hotz, G; Penkman, K E H; Collins, M J

    2009-10-01

    The poor accuracy of most current methods for estimating age-at-death in adult human skeletal remains is among the key problems facing palaeodemography. In forensic science, this problem has been solved for unburnt remains by the development of a chemical method for age estimation, using amino acid racemization in collagen extracted from dentine. Previous application of racemization methods to archaeological material has proven problematic. This study presents the application to archaeological human remains of a new age estimation method utilizing amino acid racemization in a potentially closed system-the dental enamel. The amino acid composition and extent of racemization in enamel from two Medieval cemeteries (Newcastle Blackgate and Grantham, England) and from a documented age-at-death sample from a 19th century cemetery (Spitalfriedhof St Johann, Switzerland) were determined. Alterations in the amino acid composition were detected in all populations, indicating that diagenetic change had taken place. However, in the Medieval populations, these changes did not appear to have substantially affected the relationship between racemization and age-at-death, with a strong relationship being retained between aspartic acid racemization and the morphological age estimates. In contrast, there was a poor relationship between racemization and age in the post-medieval documented age-at-death population from Switzerland. This appears to be due to leaching of amino acids post-mortem, indicating that enamel is not functioning as a perfectly closed system. Isolation of amino acids from a fraction of enamel which is less susceptible to leaching may improve the success of amino acid racemization for archaeological age estimation.

  7. A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

    Science.gov (United States)

    Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

    2015-10-30

    Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance.

  8. Serum levels of sulpiride enantiomers after oral treatment with racemic sulpiride in psychiatric patients: a pilot study.

    Science.gov (United States)

    Müller, M J; Härtter, S; Köhler, D; Hiemke, C

    2001-01-01

    Sulpiride (SULP), a substituted benzamide with high selectivity for D2-like dopamine receptors, has a chiral structure and is used in most countries as the racemate. In an open pilot study, we investigated 26 inpatients (13 female, 13 male) with schizophrenic or depressive disorder treated with SULP (mean daily dosage 64-1062 mg) administered orally, either as a monotherapy or as an add-on treatment to a stable and unchanged medication for 3-60 days. Serum levels of total SULP and of its enantiomers were measured by high-performance liquid chromatography (HPLC) procedures. Clinically relevant indicators of hepatic and renal function as well as retrospectively assessed clinical outcome parameters were correlated with serum levels of racemic SULP, L-SULP, D-SULP, and the L:D-SULP ratio. A significant correlation between mean daily dosage and serum levels of SULP, L-SULP, and D-SULP emerged (p < 0.05) which was not influenced by age, gender, diagnosis, hepatic, or renal function. The ratio of L:D-SULP serum levels was <1 (range 0.66-0.97) in all patients. A slight negative correlation between CGI improvement and the ratio of L:D-SULP (p < 0.10) and a positive correlation between racemic SULP concentrations and side-effects at endpoint was found (p < 0.05).

  9. Deracemization of Racemic Amino Acids Using (R)- and (S)-Alanine Racemase Chiral Analogues as Chiral Converters

    Energy Technology Data Exchange (ETDEWEB)

    Paik, Manjeong [Sunchon National Univ., Suncheon (Korea, Republic of); Jeon, So Hee; Lee, Wonjae [Chosun Univ., Gwangju (Korea, Republic of); Kang, Jong Seong [Chungnam National Univ., Daejeon (Korea, Republic of); Kim, Kwan Mook [Ewha Womans Univ., Seoul (Korea, Republic of)

    2014-07-15

    Our findings show that both (R)- and (S)-ARCA can be practical chiral converters for L- and D-amino acids, respectively, in the deracemization of racemic amino acids. The overall stereoselectivities of both chiral converters are generally greater than 90%. In addition, we developed chiral and achiral HPLC methods for the analysis of stereoselectivity determination. This chromatographic method proved much more accurate and convenient at determining both enantiomer and diastereomer purity than did those previously reported. Deracemization is the stereoselective process of converting a racemate into either a pure enantiomer or a mixture in which one enantiomer is present in excess.1 Previous studies have shown that (S)-alanine racemase chiral analogue (ARCA) [(S)-2-hydroxy-2'-(3-phenyluryl-benzyl)-1,1'-binaphthyl-3-carboxaldehyde], developed as a chiral convertor compound that imitates the function of alanine racemase, plays an essential role in the stereoselective conversion of amino acid. Since (S)-ARCA showed a higher stability with D-amino acids than with L-amino acids, several L-amino acids were preferentially converted to D-amino acids via (S)-ARCA/D-amino acid imine diastereomer formation. For the deracemization process undertaken in this study, we utilized both (R)-ARCA and (S)-ARCA as chiral converters, which were expected to generate L- and D-amino acids, respectively, from the starting racemic mixtures.

  10. Enantioselective Crystallization of Sodium Chlorate in the Presence of Racemic Hydrophobic Amino Acids and Static Magnetic Fields

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    María-Paz Zorzano

    2014-06-01

    Full Text Available We study the bias induced by a weak (200 mT external magnetic field on the preferred handedness of sodium chlorate crystals obtained by slow evaporation at ambient conditions of its saturated saline solution with 20 ppm of added racemic (dl hydrophobic amino acids. By applying the Fisher test to pairs of experiments with opposing magnetic field orientation we conclude, with a confidence level of 99.7%, that at the water-air interface of this saline solution there is an enantioselective magnetic interaction that acts upon racemic mixtures of hydrophobic chiral amino acids. This interaction has been observed with the three tested racemic hydrophobic amino acids: dl-Phe, dl-Try and dl-Trp, at ambient conditions and in spite of the ubiquitous chiral organic contamination. This enantioselective magnetic dependence is not observed when there is only one handedness of added chiral amino-acid, if the added amino acid is not chiral or if there is no additive. This effect has been confirmed with a double blind test. This novel experimental observation may have implications for our view of plausible initial prebiotic scenarios and of the roles of the geomagnetic field in homochirality in the biosphere.

  11. Comparative pharmacokinetics and bile transformation of R-enantiomer and racemic bambuterol after single-dose intravenous, oral administration in rats and beagle dogs.

    Science.gov (United States)

    Guan, Su; Hu, Chun-Yun; He, Meng-Ying; Yang, Ying-Ying; Tang, Yu-Xin; Chen, Jie-di; Huang, Li-Jie; Tan, Wen

    2015-12-01

    This study was to compare pharmacokinetics and bile transformation of R-enantiomer bambuterol with its racemate. Pharmacokinetics of R-enantiomer was investigated after single-dose intravenous and three doses of oral administration to rats and beagle dogs. To compare the pharmacokinetics with racemic bambuterol, the same oral doses of racemic bambuterol were also administrated; the blood and bile samples were collected by cannulation. A validated LC-MS/MS method was used to assess the level of bambuterol in plasma and bile. After single intravenous administration, no significant differences were observed between the two drugs in pharmacokinetic data. After oral dosing of R-bambuterol, the AUCs of R-enantiomer presented linear correlation. After same oral dosing of R-enantiomer and its racemate, all the pharmacokinetic parameters were equivalent. However, the clearance and apparent distribution had different results due to species and administration route difference. The bile transformation of these two compounds was similar and implicated that liver transformation accounted for the major metabolism of them. The bioavailability of R-enantiomer and racemate were comparative and relatively high in beagle dogs. Thus, R-enantiomer had a comparative pharmacokinetic profile and bile transformation with racemic bambuterol in rats and beagle dogs. These findings provided references for further clinical study.

  12. Assessing amino acid racemization variability in coral intra-crystalline protein for geochronological applications

    Science.gov (United States)

    Hendy, Erica J.; Tomiak, Peter J.; Collins, Matthew J.; Hellstrom, John; Tudhope, Alexander W.; Lough, Janice M.; Penkman, Kirsty E. H.

    2012-06-01

    Over 500 Free Amino Acid (FAA) and corresponding Total Hydrolysed Amino Acid (THAA) analyses were completed from eight independently-dated, multi-century coral cores of massive Porites sp. colonies. This dataset allows us to re-evaluate the application of amino acid racemization (AAR) for dating late Holocene coral material, 20 years after Goodfriend et al. (GCA56 (1992), 3847) first showed AAR had promise for developing chronologies in coral cores. This re-assessment incorporates recent method improvements, including measurement by RP-HPLC, new quality control approaches (e.g. sampling and sub-sampling protocols, statistically-based data screening criteria), and cleaning steps to isolate the intra-crystalline skeletal protein. We show that the removal of the extra-crystalline contaminants and matrix protein is the most critical step for reproducible results and recommend a protocol of bleaching samples in NaOCl for 48 h to maximise removal of open system proteins while minimising the induced racemization. We demonstrate that AAR follows closed system behaviour in the intra-crystalline fraction of the coral skeletal proteins. Our study is the first to assess the natural variability in intra-crystalline AAR between colonies, and we use coral cores taken from the Great Barrier Reef, Australia, and Jarvis Island in the equatorial Pacific to explore variability associated with different environmental conditions and thermal histories. Chronologies were developed from THAA Asx D/L, Ala D/L, Glx D/L and FAA Asx D/L for each core and least squares Monte Carlo modelling applied in order to quantify uncertainty of AAR age determinations and assess the level of dating resolution possible over the last 5 centuries. AAR within colonies follow consistent stratigraphic aging. However, there are systematic differences in rates between the colonies, which would preclude direct comparison from one colony to another for accurate age estimation. When AAR age models are developed from

  13. Highly enantioselective esterification of racemic ibuprofen in a packed bed reactor using immobilised Rhizomucor miehei lipase.

    Science.gov (United States)

    Sánchez; Valero; Lafuente; Solà

    2000-07-01

    A systematic study of the enantioselective resolution of ibuprofen by commercial Rhizomucor miehei lipase (Lipozyme(R) IM20) has been carried out using isooctane as solvent and butanol as esterificating agent. The main variables controlling the process (temperature, ibuprofen concentration, ratio butanol:ibuprofen) have been studied using an orthogonal full factorial experimental design, in which the selected objective function was enantioselectivity. This strategy has resulted in a polynomial function that describes the process. By optimizing this function, optimal conditions for carrying out the esterification of racemic ibuprofen have been determined. Under these conditions, enantiomeric excess and total conversion values were 93.8% and 49.9%, respectively, and the enantioselectivity was 113 after 112 h of reaction. These conditions have been considered in the design of a continuous reactor to scale up the process. The esterification of ibuprofen was properly described by pseudo first-order kinetics. Thus, a packed bed reactor operating as a plug-flow reactor (PFR) is the most appropriate in terms of minimizing the residence time compared with a continuous stirred tank reactor (CSTR) to achieve the same final conversion. This reactor shows a similar behavior in terms of enantioselectivity, enantiomeric excess, and conversion when compared with batch reactors. A residence-time distribution (RTD) shows that the flow model is essentially a plug flow with a slight nonsymmetrical axial dispersion (Peclet number = 43), which was also corroborated by the model of CSTR in series. The stability of the system (up to 100 h) and the possibility of reutilization of the enzyme (up to four times) lead to consider this reactor as a suitable configuration for scale up of the process.

  14. The pharmacokinetics of racemic MDPV and its (R) and (S) enantiomers in female and male rats.

    Science.gov (United States)

    Hambuchen, Michael D; Hendrickson, Howard P; Gunnell, Melinda G; McClenahan, Samantha J; Ewing, Laura E; Gibson, Dillon M; Berquist, Michael D; Owens, S Michael

    2017-10-01

    These studies investigated the serum pharmacokinetic (PK) profile of racemic (3,4)-methylenedioxypyrovalerone [(R,S)-MDPV)] and its (R)- and (S)-enantiomers in female and male Sprague Dawley rats. Intravenous (R,S)-MDPV (3 and 5.6mg/kg) and single enantiomer of (R)- and (S)-MDPV (1.5mg/kg) were administered to both sexes for PK studies. Intraperitoneal (ip) bioavailability was determined at 3mg/kg (R,S)-MDPV. Locomotor activity studies were conducted after ip treatment with saline and 0.3-5.6mg/kg of (R,S)-MDPV. PK values after iv (R,S)-MDPV showed a significant (pMDPV at both (R,S)-MDPV doses. The female S/R enantiomeric ratios for area under the concentration time curve (AUCinf) and clearance were significantly lower and higher, respectively, than values determined in males. Importantly, there was no evidence of in vivo inversion of (R)-MDPV or (S)-MDPV to its antipode. There were, however, significant sex-dependent differences in volume of distribution after administration of the (R)-enantiomer. Bioavailability studies of ip (R,S)-MDPV showed greater variability and significantly greater bioavailability in male rats. Accordingly, there was a significantly greater maximal distance traveled measurement in male rats at a 3.0mg/kg dose. PK sex differences in (R,S)-MDPV and enantiomers were most apparent in volume of distribution, which could be caused by differences in drug blood and tissue protein binding. The increased magnitude and variance in ip bioavailability in male compared to female rats could lead to sex-dependent differences in the pharmacological action caused by active enantiomer (S)-MDPV. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Chiral fluorinated α-sulfonyl carbanions: enantioselective synthesis and electrophilic capture, racemization dynamics, and structure.

    Science.gov (United States)

    Hellmann, Gunther; Hack, Achim; Thiemermann, Eric; Luche, Olaf; Raabe, Gerhard; Gais, Hans-Joachim

    2013-03-18

    Enantiomerically pure triflones R(1) CH(R(2) )SO2 CF3 have been synthesized starting from the corresponding chiral alcohols via thiols and trifluoromethylsulfanes. Key steps of the syntheses of the sulfanes are the photochemical trifluoromethylation of the thiols with CF3 Hal (Hal=halide) or substitution of alkoxyphosphinediamines with CF3 SSCF3 . The deprotonation of RCH(Me)SO2 CF3 (R=CH2 Ph, iHex) with nBuLi with the formation of salts [RC(Me)SO2 CF3 ]Li and their electrophilic capture both occurred with high enantioselectivities. Displacement of the SO2 CF3 group of (S)-MeOCH2 C(Me)(CH2 Ph)SO2 CF3 (95 % ee) by an ethyl group through the reaction with AlEt3 gave alkane MeOCH2 C(Me)(CH2 Ph)Et of 96 % ee. Racemization of salts [R(1) C(R(2) )SO2 CF3 ]Li follows first-order kinetics and is mainly an enthalpic process with small negative activation entropy as revealed by polarimetry and dynamic NMR (DNMR) spectroscopy. This is in accordance with a Cα S bond rotation as the rate-determining step. Lithium α-(S)-trifluoromethyl- and α-(S)-nonafluorobutylsulfonyl carbanion salts have a much higher racemization barrier than the corresponding α-(S)-tert-butylsulfonyl carbanion salts. Whereas [PhCH2 C(Me)SO2 tBu]Li/DMPU (DMPU = dimethylpropylurea) has a half-life of racemization at -105 °C of 2.4 h, that of [PhCH2 C(Me)SO2 CF3 ]Li at -78 °C is 30 d. DNMR spectroscopy of amides (PhCH2 )2 NSO2 CF3 and (PhCH2 )N(Ph)SO2 CF3 gave NS rotational barriers that seem to be distinctly higher than those of nonfluorinated sulfonamides. NMR spectroscopy of [PhCH2 C(Ph)SO2 R]M (M=Li, K, NBu4 ; R=CF3 , tBu) shows for both salts a confinement of the negative charge mainly to the Cα atom and a significant benzylic stabilization that is weaker in the trifluoromethylsulfonyl carbanion. According to crystal structure analyses, the carbanions of salts {[PhCH2 C(Ph)SO2 CF3 ]Li⋅L}2 (L=2 THF, tetramethylethylenediamine (TMEDA)) and [PhCH2 C(Ph)SO2 CF3 ]NBu4 have

  16. Pharmacological characterization and binding modes of novel racemic and optically active phenylalanine-based antagonists of AMPA receptors

    DEFF Research Database (Denmark)

    Szymańska, Ewa; Nielsen, Birgitte; Johansen, Tommy Nørskov

    2017-01-01

    In order to map out molecular determinants for the competitive blockade of AMPA receptor subtypes, a series of racemic aryl-substituted phenylalanines was synthesized and pharmacologically characterized in vitro at native rat ionotropic glutamate receptors. Most of the compounds showed micromolar...... affinity and preference for AMPA receptors. Individual stereoisomers of selected compounds were further evaluated at recombinant homomeric rat GluA2 and GluA3 receptors. The most potent compound, (–)-2-amino-3-(6-chloro-2',5'-dihydroxy-5-nitro-[1,1'-biphenyl]-3-yl)propanoic acid, the expected R...

  17. Enantioselective esterification of racemic ibuprofen in isooctane by immobilized lipase on cellulose acetate-titanium iso-propoxide gel fiber.

    Science.gov (United States)

    Ikeda, Yuko; Kurokawa, Youichi

    2002-01-01

    Lipase (Candida rugosa) was entrap-immobilized on cellulose acetate-titanium iso-propoxide gel fiber by the sol-gel method. The immobilized lipase was used for the direct synthesis of (S)-ibuprofen ester from racemic ibuprofen using propyl alcohol as an acyl acceptor in isooctane. The activity of the immobilized lipase was decreased to about 10-20% that of native lipase. However, the reaction was more enantioselective compared to that with native lipase. The stability for repeated use was improved by immobilization.

  18. Nickel-catalyzed enantioselective cross-couplings of racemic secondary electrophiles that bear an oxygen leaving group.

    Science.gov (United States)

    Oelke, Alexander J; Sun, Jianwei; Fu, Gregory C

    2012-02-15

    To date, effective nickel-catalyzed enantioselective cross-couplings of alkyl electrophiles that bear oxygen leaving groups have been limited to reactions of allylic alcohol derivatives with Grignard reagents. In this Communication, we establish that, in the presence of a nickel/pybox catalyst, a variety of racemic propargylic carbonates are suitable partners for asymmetric couplings with organozinc reagents. The method is compatible with an array of functional groups and utilizes commercially available catalyst components. The development of a versatile nickel-catalyzed enantioselective cross-coupling process for electrophiles that bear a leaving group other than a halide adds a significant new dimension to the scope of these reactions.

  19. Simultaneous Adjustment of Size and Helical Sense of Chiral Nanospheres and Nanotubes Derived from an Axially Racemic Poly(phenylacetylene).

    Science.gov (United States)

    Arias, Sandra; Núñez-Martínez, Manuel; Quiñoá, Emilio; Riguera, Ricardo; Freire, Félix

    2017-01-01

    Nanospheres and nanotubes with full control of their size and helical sense are obtained in chloroform from the axially racemic chiral poly(phenylacetylene) poly-(R)-1 using either Ag(+) as both chiral inducer and cross-linking agent or Na(+) as chiral inducer and Ag(+) as cross-linking agent. The size is tuned by the polymer/ion ratio while the helical sense is modulated by the polymer/cosolvent (i.e., MeCN) ratio. In this way, the helicity and the size of the nanoparticles can be easily interconverted by very simple experimental changes.

  20. A randomized, double-blind, placebo-controlled study to investigate the safety, tolerability, and pharmacokinetics of single enantiomer (+)-mefloquine compared with racemic mefloquine in healthy persons.

    Science.gov (United States)

    Tansley, Robert; Lotharius, Julie; Priestley, Anthony; Bull, Fiona; Duparc, Stephan; Möhrle, Jörg

    2010-12-01

    Racemic mefloquine is a highly effective antimalarial whose clinical utility has been compromised by its association with neuropsychiatric and gastrointestinal side effects. It is hypothesized that the cause of the side effects may reside in the (-) enantiomer. We sought to compare the safety, tolerability and pharmacokinetic profile of (+)-mefloquine with racemic mefloquine in a randomized, ascending-dose, double-blind, active and placebo-controlled, parallel cohort study in healthy male and female adult volunteers. Although differing in its manifestations, both study drugs displayed a substantially worse tolerability profile compared with placebo. The systemic clearance was slower for (-)-mefloquine than (+)-mefloquine. Thus, (+)-mefloquine has a different safety and tolerability profile compared with racemic mefloquine but its global safety profile is not superior and replacement of the currently used antimalarial drug with (+)-mefloquine is not warranted.

  1. The importance of screening solid-state phases of a racemic modification of a chiral drug: thermodynamic and structural characterization of solid-state phases of etiracetam.

    Science.gov (United States)

    Herman, Christelle; Vermylen, Valérie; Norberg, Bernadette; Wouters, Johan; Leyssens, Tom

    2013-08-01

    In this contribution different solid-state forms of the racemic compound (RS)-2-(2-oxo-pyrrolidin-1yl)-butyramide are studied from a structural and thermal point of view. Three different solid-state phases were identified, including two polymorphs and one hydrate phase. Comparison is made with the structure of the (S)-enantiomer, for which only one solid-state phase is known. The basic structural motif found in both polymorphs of the racemic compound is similar, but the basic motif observed for the hydrate differs. These synthons could in principle be used in future polymorph prediction studies to screen for possible alternative forms of the enantiopure compound. Based on the structure of the hydrate, further efforts should therefore be made in order to identify a hydrate structure of the enantiopure compound. Studying the different phases of a racemic compound can therefore help to guide polymorphic screening of an enantiopure compound.

  2. Racemic ketamine in comparison to S-ketamine in combination with azaperone and butorphanol for castration of pigs.

    Science.gov (United States)

    Bettschart-Wolfensberger, R; Stauffer, S; Hässig, M; Flaherty, D; Ringer, S K

    2013-12-01

    In this prospective blinded randomised study, 28 male 9 week old pigs of bodyweight 25 kg, were anaesthetised for castration using 5 mg/kg azaperone, 0.2 mg/kg butorphanol and 0.4 mg/kg meloxicam, in conjunction with either 15 mg/kg racemic ketamine (Keta-Race) or 9 mg/kg S-ketamine (S-Keta), all drugs being injected intramuscularly. Anaesthesia induction, maintenance and recovery were timed and scored. Insufficient anaesthesia was supplemented with ¼ the initial dose of ketamine or S-ketamine, respectively, administered intravenously. A t-test was utilised for analysis of timings, and, for repeated recovery time data, ANOVA was used. In relation to quantification and timing of supplemental drug doses, a chi square test was used and the scoring was analysed by two sample Wilcoxon rank-sum test. Ketamine re-dosing was required in 23 animals on a total of 46 occasions distributed evenly throughout both groups. The only group differences occurred during recovery, with the S-Keta group showing earlier movements, sternal recumbency and ability to stand. Three pigs in each group showed muscle fasciculations during the recovery period, while an additional two animals of the Keta-Race group exhibited marked and unacceptable paddling in recovery. In conclusion, S-ketamine at a dose rate of 60 % of that of racemic ketamine induced comparable anaesthesia for castration in pigs, but with superior recovery characteristics.

  3. A new and recyclable system based on tropin ionic liquids for resolution of several racemic amino acids.

    Science.gov (United States)

    Wang, Zhixia; Hou, Zhenbo; Yao, Shun; Lin, Min; Song, Hang

    2017-04-01

    A new, recyclable solid-liquid resolution system was developed based on tropin ionic liquids [CnDTr][L-Pro]2 for the enantiomeric resolution of racemic phenylalanine and other α-substituted carboxylic acids including tryptophan, tyrosine, benzene glycine and mandelic acid. With racemic phenylalanine as resolution model, effect factors were investigated for better resolution conditions. On the conditions, some efficient resolution were achieved, for instance the e.e. (98%) and product yield (76%) in solid phase for phenylalanine, and the e.e. 99.71% in solid phase for tryptophan. Chiral product was verified with fourier transform infrared spectroscopy (FT-IR), Raman spectrum, thermal gravity analysis (TG), elemental analysis (EA) and chiral HPLC. Further, the resolution mechanism was studied with computer molecular dynamic simulations and UV-vis. The resolution was closely related to the formation of complexes (L-Phe-Cu(Ⅱ)-L-pro(-)) and the spatial configuration of D/L-Phe. The system is characteristic of high resolution, no organic solvent, easy isolation of solid-liquid and recycle of all chemical materials as much as possible.

  4. Asymmetric aminolytic kinetic resolution of racemic epoxides using recyclable chiral polymeric Co(III)-salen complexes: a protocol for total utilization of racemic epoxide in the synthesis of (R)-Naftopidil and (S)-Propranolol.

    Science.gov (United States)

    Kumar, Manish; Kureshy, Rukhsana I; Shah, Arpan K; Das, Anjan; Khan, Noor-ul H; Abdi, Sayed H R; Bajaj, Hari C

    2013-09-20

    Chiral polymeric Co(III) salen complexes with chiral ((R)/(S)-BINOL, diethyl tartrate) and achiral (piperazine and trigol) linkers with varying stereogenic centers were synthesized for the first time and used as catalysts for aminolytic kinetic resolution (AKR) of a variety of terminal epoxides and glycidyl ethers to get enantio-pure epoxides (ee, 99%) and N-protected β-amino alcohols (ee, 99%) with quantitative yield in 16 h at RT under optimized reaction conditions. This protocol was also used for the synthesis of two enantiomerically pure drug molecules (R)-Naftopidil (α1-blocker) and (S)-Propranolol (β-blocker) as a key step via AKR of single racemic naphthylglycidyl ether with Boc-protected isoproylamine with 100% epoxide utilization at 1 g level. The catalyst 1 was successfully recycled for a number of times.

  5. Comparative clinical trial of S-pantoprazole versus racemic pantoprazole in the treatment of gastro-esophageal reflux disease

    Institute of Scientific and Technical Information of China (English)

    Vikas G Pai; Nitin V Pai; Hemant P Thacker; Jaisingh K Shinde; Vijay P Mandora; Subhash S Erram

    2006-01-01

    AIM: To compare the efficacy and tolerability of S-pantoprazole (20 mg once a day) versus racemic Pantoprazole (40 mg once a day) in the treatment of gastroesophageal reflux disease (GERD).METHODS: This multi-centre, randomized, double-blind clinical trial consisted of 369 patients of either sex suffering from GERD. Patients were randomly assigned to receive either one tablet (20 mg) of S-pantoprazole once a day (test group) or 40 mg racemic pantoprazole once a day (reference group) for 28 d. Patients were evaluated for reduction in baseline on d 0, GERD symptom score on d 14 and 28, occurrence of any adverse effect during the course of therapy. Gastrointestinal (GI) endoscopy was performed in 54 patients enrolled at one of the study centers at baseline and on d 28.RESULTS: Significant reduction in the scores (mean and median) for heart burn (P < 0.0001), acid regurgitation (P < 0.0001), bloating (P < 0.0001), nausea (P < 0.0001)and dysphagia (P < 0.001) was achieved in both groups on d 14 with further reduction on continuing the therapy till 28 d. There was a statistically significant difference in the proportion of patients showing improvement in acid regurgitation and bloating on d 14 and 28 (P = 0.004for acid regurgitation; P = 0.03 for bloating) and heart burn on d 28 (P = 0.01) between the two groups, with a higher proportion in the test group than in the reference group. Absolute risk reductions for heartburn/acid regurgitation/bloating were approximately 15% on d 14 and 10% on d 28. The relative risk reductions were 26%-33% on d 14 and 15% on d 28. GI endoscopy showed no significant difference in healing of esophagitis (P= 1) and gastric erosions (P = 0.27) between the two groups. None of the patients in either group reported any adverse effect during the course of therapy.CONCLUSION: In GERD, S-pantoprazole (20 mg) is more effective than racemic pantoprazole (40 mg) in improving symptoms of heartburn, acid regurgitation,bloating and equally

  6. Aqueous microwave-assisted solid-phase peptide synthesis using Fmoc strategy. III: racemization studies and water-based synthesis of histidine-containing peptides.

    Science.gov (United States)

    Hojo, Keiko; Shinozaki, Natsuki; Hidaka, Koushi; Tsuda, Yuko; Fukumori, Yoshinobu; Ichikawa, Hideki; Wade, John D

    2014-10-01

    In this study, we describe the first aqueous microwave-assisted synthesis of histidine-containing peptides in high purity and with low racemization. We have previously shown the effectiveness of our synthesis methodology for peptides including difficult sequences using water-dispersible 9-fluorenylmethoxycarbonyl-amino acid nanoparticles. It is an organic solvent-free, environmentally friendly method for chemical peptide synthesis. Here, we studied the racemization of histidine during an aqueous-based coupling reaction with microwave irradiation. Under our microwave-assisted protocol using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, the coupling reaction can be efficiently performed with low levels of racemization of histidine. Application of this water-based microwave-assisted protocol with water-dispersible 9-fluorenylmethoxycarbonyl-amino acid nanoparticles led to the successful synthesis of the histidine-containing hexapeptide neuropeptide W-30 (10-15), Tyr-His-Thr-Val-Gly-Arg-NH₂, in high yield and with greatly reduced histidine racemization.

  7. Intermixed Adatom and Surface‐Bound Adsorbates in Regular Self‐Assembled Monolayers of Racemic 2‐Butanethiol on Au(111)

    DEFF Research Database (Denmark)

    Ouyang, Runhai; Yan, Jiawei; Jensen, Palle Skovhus;

    2015-01-01

    In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self‐assembled monolayer (SAM) of racemic 2‐butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as tw...

  8. Titanocene(III) chloride mediated radical induced addition-elimination route to the synthesis of racemic and optically active trisubstituted tetrahydrofurans: Formal synthesis of magnofargesin and 7'-epimagnofargesin

    Indian Academy of Sciences (India)

    P CHAKRABORTY; S K MANDAL; S C ROY

    2016-07-01

    Titanocene(III) Chloride mediated radical induced synthesis of 4-benzylidene substituted tetrahydrofuran, a typical lignan skeleton, has been accomplished in good yield through addition-elimination route in racemic as well as in optically active forms. The method has been applied to the synthesis of furano lignans, magnofargesin (1) and 7'-epimagnofargesin (2) in optically active forms.

  9. Temperature effects on the chromatographic behaviour of racemic 2-amidotetralins on a Whelk-O 1 stationary phase in super- and subcritical fluid chromatography

    NARCIS (Netherlands)

    Selditz, U; Copinga, S; Grol, CJ; Franke, JP; de Zeeuw, RA; Wikstrom, H; Gyllenhaal, O

    1999-01-01

    The chromatographic behaviour of thirty structurally related racemic 2-amidotetralins on a cis-(3R, 4S)-Whelk-O 1 stationary phase was investigated at five different temperatures between 50 and -15 degrees C using super- or subscritical fluid chromatography (SFC/SubFC). Generally, low selectivity fa

  10. Racemization of the Succinimide Intermediate Formed in Proteins and Peptides: A Computational Study of the Mechanism Catalyzed by Dihydrogen Phosphate Ion

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2016-10-01

    Full Text Available In proteins and peptides, d-aspartic acid (d-Asp and d-β-Asp residues can be spontaneously formed via racemization of the succinimide intermediate formed from l-Asp and l-asparagine (l-Asn residues. These biologically uncommon amino acid residues are known to have relevance to aging and pathologies. Although nonenzymatic, the succinimide racemization will not occur without a catalyst at room or biological temperature. In the present study, we computationally investigated the mechanism of succinimide racemization catalyzed by dihydrogen phosphate ion, H2PO4−, by B3LYP/6-31+G(d,p density functional theory calculations, using a model compound in which an aminosuccinyl (Asu residue is capped with acetyl (Ace and NCH3 (Nme groups on the N- and C-termini, respectively (Ace–Asu–Nme. It was shown that an H2PO4− ion can catalyze the enolization of the Hα–Cα–C=O portion of the Asu residue by acting as a proton-transfer mediator. The resulting complex between the enol form and H2PO4− corresponds to a very flat intermediate region on the potential energy surface lying between the initial reactant complex and its mirror-image geometry. The calculated activation barrier (18.8 kcal·mol−1 after corrections for the zero-point energy and the Gibbs energy of hydration for the enolization was consistent with the experimental activation energies of Asp racemization.

  11. Racemization of the Succinimide Intermediate Formed in Proteins and Peptides: A Computational Study of the Mechanism Catalyzed by Dihydrogen Phosphate Ion

    Science.gov (United States)

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2016-01-01

    In proteins and peptides, d-aspartic acid (d-Asp) and d-β-Asp residues can be spontaneously formed via racemization of the succinimide intermediate formed from l-Asp and l-asparagine (l-Asn) residues. These biologically uncommon amino acid residues are known to have relevance to aging and pathologies. Although nonenzymatic, the succinimide racemization will not occur without a catalyst at room or biological temperature. In the present study, we computationally investigated the mechanism of succinimide racemization catalyzed by dihydrogen phosphate ion, H2PO4−, by B3LYP/6-31+G(d,p) density functional theory calculations, using a model compound in which an aminosuccinyl (Asu) residue is capped with acetyl (Ace) and NCH3 (Nme) groups on the N- and C-termini, respectively (Ace–Asu–Nme). It was shown that an H2PO4− ion can catalyze the enolization of the Hα–Cα–C=O portion of the Asu residue by acting as a proton-transfer mediator. The resulting complex between the enol form and H2PO4− corresponds to a very flat intermediate region on the potential energy surface lying between the initial reactant complex and its mirror-image geometry. The calculated activation barrier (18.8 kcal·mol−1 after corrections for the zero-point energy and the Gibbs energy of hydration) for the enolization was consistent with the experimental activation energies of Asp racemization. PMID:27735868

  12. Biocatalytic synthesis of (R)-(-)-mandelic acid from racemic mandelonitrile by a newly isolated nitrilase-producer Alcaligenes sp. ECU0401

    Institute of Scientific and Technical Information of China (English)

    Yu Cai He; Jian He Xu; Yi Xu; Li Ming Ouyang; Jiang Pan

    2007-01-01

    By using acetonitrile as the sole nitrogen source, a microbial strain with high nitrilase activity, named as Alcaligenes sp.ECU0401, was newly isolated from soil, which could enantioselectively transform racemic mandelonitrile into (R)-(-)-mandelic acid, with an enantiomeric excess of>99.9%.

  13. Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

    Directory of Open Access Journals (Sweden)

    Sara J. Krivickas

    2015-09-01

    Full Text Available Chiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithiotetrathiafulvalene (BEDT-TTF derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl(methyl-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ21-[(S,S-2]3[(R,R-2]3(ClO42 and the chiral salt α’-[(R,R-2]ClO4(H2O were carried out. In the former θ21-[(S,S-2]3[(R,R-2]3(ClO42, there are two sets of three crystallographically independent donor molecules [(S,S-2]2[(R,R-2] in a unit cell, where the two sets are related by an inversion center. The latter α’-[(R,R-2]ClO4(H2O is the chiral salt with included solvent H2O, which is not isostructural with the reported chiral salt α’-[(S,S-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4− anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å were observed in these crystals between electron donor molecules, anions, and included H2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with Ea = 86 meV for θ21-[(S,S-2]3[(R,R-2]3(ClO42 and 0.6 ohm cm with Ea = 140 meV for α'-[(R,R-2]2ClO4(H2O, respectively. The variety of donor arrangements

  14. Intermixed adatom and surface-bound adsorbates in regular self-assembled monolayers of racemic 2-butanethiol on Au(111).

    Science.gov (United States)

    Ouyang, Runhai; Yan, Jiawei; Jensen, Palle S; Ascic, Erhad; Gan, Shiyu; Tanner, David; Mao, Bingwei; Niu, Li; Zhang, Jingdong; Tang, Chunguang; Hush, Noel S; Reimers, Jeffrey R; Ulstrup, Jens

    2015-04-07

    In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self-assembled monolayer (SAM) of racemic 2-butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as two RSAuSR adatom-bound motifs plus two RS species bound directly to face-centered-cubic and hexagonally close-packed sites. This is the first time that these competing head-group arrangements have been observed in the same ordered SAM. Such unusual packing is favored as it facilitates SAMs with anomalously high coverage (30%), much larger than that for enantiomerically resolved 2-butanethiol or secondary-branched butanethiol (25%) and near that for linear-chain 1-butanethiol (33%).

  15. Catalytic asymmetric synthesis of secondary nitriles via stereoconvergent Negishi arylations and alkenylations of racemic α-bromonitriles.

    Science.gov (United States)

    Choi, Junwon; Fu, Gregory C

    2012-06-06

    The first method for the stereoconvergent cross-coupling of racemic α-halonitriles is described, specifically, nickel-catalyzed Negishi arylations and alkenylations that furnish an array of enantioenriched α-arylnitriles and allylic nitriles, respectively. Noteworthy features of this investigation include: the highly enantioselective synthesis of α-alkyl-α-aryl nitriles that bear secondary α-alkyl substituents; the first examples of the use of alkenylzinc reagents in stereoconvergent Negishi reactions of alkyl electrophiles; demonstration of the utility of a new family of ligands for asymmetric Negishi cross-couplings (a bidentate bis(oxazoline), rather than a tridentate pybox); in the case of arylzinc reagents, carbon-carbon bond formation at a remarkably low temperature (-78 °C), the lowest reported to date for an enantioselective cross-coupling of an alkyl electrophile; a mechanistic dichotomy between Negishi reactions of an unactivated versus an activated secondary alkyl bromide.

  16. Liquid chromatographic resolution of racemic 2-oxazolidinones and their analogs on seven pirkle-type chiral stationary phases

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jeong Jae [Dept. of Chemistry, Graduate School, Kyungpook National University, Daegu (Korea, Republic of); Hyun, Myung Ho [Dept. of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Pusan (Korea, Republic of); Amstrong, Daniel W.; Breitbach, Zachary S. [Dept. of Chemistry, University of Texas at Arlington, Arlington (United States)

    2015-02-15

    Oxazolidinones are mainly used as antimicrobials and have an antibacterial effect due to their action as protein synthesis inhibitors, wherein they target an early step involving the binding of N-formylmethionyl-tRNA to the ribosome. Various oxazolidinones have been used as antibiotics with usually the (S)-form being active. 2–5 The chiral separation of nonoxazolidinone samples has been previously reported. Separation of DUP-105, ZTR-5, and 3-amino2-oxazolidinone derivatives was performed on polysaccharide columns. All the racemic and optically active samples were dissolved in methylene chloride or methanol (usually 2.5 mg/mL) and then used for resolution on CSPs. In most cases, an injection volume of 5 μL was used; however, it was varied slightly according to the size of the chromatographic peaks that corresponded to the two enantiomers.

  17. (±-Pestalachloride D, an Antibacterial Racemate of Chlorinated Benzophenone Derivative from a Soft Coral-Derived Fungus Pestalotiopsis sp.

    Directory of Open Access Journals (Sweden)

    Dong-Sheng Deng

    2013-03-01

    Full Text Available A new antibacterial chlorinated benzophenone derivative, (±-pestalachloride D (1, along with a related analog, (±-pestalachloride C (2, was recently isolated from the marine-derived fungus Pestalotiopsis sp. isolated from a soft coral Sarcophyton sp. collected from Yongxing Island in the South China Sea. Both chiral HPLC analysis and single-crystal X-ray data indicated that 1 is a racemic mixture. Interestingly, 1 did not exhibit any effect in the zebrafish embryo teratogenicity assay, while 2 led to abnormal growth. The potential impact on zebrafish embryo growth is discussed based on their crystal structures. The main difference of crystal structures between 1 and 2 is that the six-member non-aromatic ring (O4, C10, C9, C8, C2′, and C3′ in 1 exhibits a distorted chair conformation, while 2 shows a distorted boat conformation. Moreover, compounds 1 and 2 both exhibited moderate antibacterial activity.

  18. Evaluation of dispersion state of the two racemic compounds of troglitazone in pharmaceutical granules using IR-to-THz imaging

    Science.gov (United States)

    Yonemochi, Etsuo; Furuyama, Naho; Bunko, Mika; Moriwaki, Taro; Ikemoto, Yuka; Terada, Katsuhide

    2008-05-01

    Troglitazone exists as four isomers in equal amount and these isomers compose two racemic compounds, RR/SS and RS/SR. The objective of this study was to discriminate between the racemic compounds and between the crystal and amorphous forms of troglitazone in solid dispersions (SDs) using IR-to-THz imaging. SDs of troglitazone with polyvinylpyrrolidone (PVP, carrier) were prepared by the closed melting method. SDs were heated at various temperatures and water content. The mid-to-far infrared measurements for the powder samples were performed by using the synchrotron radiation source at the BL43IR in SPring-8. Crystalline RR/SS (L) and RS/SR (H) showed different spectra, that is, each form had a specific peak, respectively. However, amorphous forms prepared from each crystalline form exhibited the same spectra. Using the chemo-metric analysis, the existing component was decided in each pixel and the distribution of crystalline L, H and amorphous troglitazone in SDs could be illustrated. For the sample heated at 105 °C, 75%RH, scattered plots of H and amorphous against PVP showed the trend for H was negative; on the other hand, amorphous showed positive correlation. This result suggested that H existed separately, whereas amorphous would be dissolved in PVP. Based on these evaluations, it was clear that the physical state and distribution of troglitazone in SDs, including the discrimination between L, H, and amorphous, reflect the preparation conditions. Chemical imaging can observe a difference in the dispersed state of drug and ingredient in a visible image by performing statistical processing.

  19. Adsorption of nicotine on different zeolite types, from aqueous solutions

    Directory of Open Access Journals (Sweden)

    Stošić Dušan K.

    2007-01-01

    Full Text Available The plant alkaloid, nicotine, is a strongly toxic heterocyclic compound: the lethal dose for an adult human being (40-60 mg is importantly lower in comparison with the other known poisons such as arsenic or strychni­ne. Cigarettes represent "the most toxic and addictive form of nicotine". Besides the negative effects of nicotine on public health produced by self-administration, recently another potentially very dangerous effect has been recognized: because of its miscibility with water, nicotine can be found in industrial wastewaters, and consequently, in groundwater. Therefore, the problem of nicotine removal from aqueous solutions has became an interesting topic. In this work, the removal of nicotine has been probed by adsorption on solid materials. Adsorption of nicotine on different zeolites (clinoptilolite, ZSM-5 and β zeolite and on activated carbon was investigated from aqueous solutions, at 298 K. The obtained results are presented as adsorption isotherms: the amount of adsorbed nicotine as a function of equilibrium concentration. These data were obtained from the residual amount of nicotine in the aqueous phase, by the use of UV spectroscopy. The highest amounts of adsorbed nicotine was found for activated carbon and p zeolite (~ mmol·g-1. The attempt to modify the adsorption properties of ZSM-5 zeolite has been also done: ZSM-5 was modified by ion-exchange with VIII group metal (Cu2+ and Fe3+. In addition, the adsorption of nicotine on ZSM-5 zeolite with different Si/Al ratios has been done. It has been noticed that ion-exchange did not improve the adsorption possibilities, while the adsorption was importantly lower in the case of higher silicon content in ZMS-5 structure. 13C NMR spectra were collected for suspensions formed of solid adsorbent and aqueous solution of nicotine; in this way, the part of nicotine molecule which is most probably connected with the adsorbent was recognized.

  20. Percutaneous permeation of enantiomers and racemates of chiral drugs and prediction of their flux ratios using thermal data: a pharmaceutical perspective.

    Science.gov (United States)

    Afouna, Mohsen I; Fincher, Timothy K; Khan, Mansoor A; Reddy, Indra K

    2003-05-15

    Albeit pharmacological, pharmacokinetic, and toxicological differences between enantiomeric pairs or between the pure enantiomers and racemate of chiral drugs are known to exist for decades, we are just beginning to realize that there are apparent differences between these species with respect to their percutaneous permeation as well. Such differences in permeation are likely to be enhanced when chiral drugs are formulated with chiral excipients, necessitating a careful assessment of the effect of formulation excipients on the permeation as well as the overall therapeutic outcomes. The in vitro transport data from the preclinical investigations, using laboratory animal models and/or in vitro cell culture systems, must be carefully validated in vivo as there are differences between these models and the human skin. Mathematical models such as MTMT that utilize the interdependence of certain physicochemical characteristics and percutaneous permeability have a predictive value in assessing the flux behavior of enantiomers and racemates.

  1. Single-walled carbon nanotube-based polymer monoliths for the enantioselective nano-liquid chromatographic separation of racemic pharmaceuticals.

    Science.gov (United States)

    Ahmed, Marwa; Yajadda, Mir Massoud Aghili; Han, Zhao Jun; Su, Dawei; Wang, Guoxiu; Ostrikov, Kostya Ken; Ghanem, Ashraf

    2014-09-19

    Single-walled carbon nanotubes were encapsulated into different polymer-based monolithic backbones. The polymer monoliths were prepared via the copolymerization of 20% monomers, glycidyl methacrylate, 20% ethylene glycol dimethacrylate and 60% porogens (36% 1-propanol, 18% 1,4-butanediol) or 16.4% monomers (16% butyl methacrylate, 0.4% sulfopropyl methacrylate), 23.6% ethylene glycol dimethacrylate and 60% porogens (36% 1-propanol, 18% 1,4-butanediol) along with 6% single-walled carbon nanotubes aqueous suspension. The effect of single-walled carbon nanotubes on the chiral separation of twelve classes of pharmaceutical racemates namely; α- and β-blockers, antiinflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs and antiarrhythmic drugs was investigated. The enantioselective separation was carried out under multimodal elution to explore the chiral recognition capabilities of single-walled carbon nanotubes using reversed phase, polar organic and normal phase chromatographic conditions using nano-liquid chromatography. Baseline separation was achieved for celiprolol, chlorpheniramine, etozoline, nomifensine and sulconazole under multimodal elution conditions. Satisfactory repeatability was achieved through run-to-run, column-to-column and batch-to-batch investigations. Our findings demonstrate that single-walled carbon nanotubes represent a promising stationary phase for the chiral separation and may open the field for a new class of chiral selectors.

  2. Molecular design of DABNTf as a highly efficient resolving reagent for racemic Pd complex with Tropos biphenylphosphine (BIPHEP) ligand: circular dichroism (CD) spectra of enantiopure BIPHEP-Pd complex.

    Science.gov (United States)

    Mikami, Koichi; Yusa, Yukinori; Aikawa, Kohsuke; Hatano, Manabu

    2003-01-01

    The racemic Pd complexes with chirally flexible (tropos) biphenylphosphine (BIPHEP) ligands can be resolved but transformed into the enantio- and diastereo-pure complex. The enantiopure metal complex of BIPHEP ligand is thus obtained through enantiomer-selective complexation of a racemic BIPHEP-Pd complex with enantiopure 1,1'-binaphthyl-2,2'-di(triflyl)amide, DABNTf. The differential CD spectra of the enantiopure BIPHEP-Pd complex is also reported. Copyright 2002 Wiley-Liss, Inc.

  3. High resolution of racemic phenylalanine with dication imidazolium-based chiral ionic liquids in a solid-liquid two-phase system.

    Science.gov (United States)

    Huang, Xiaoxia; Wu, Haoran; Wang, Zhixia; Luo, Yingjie; Song, Hang

    2017-01-06

    A novel solid-liquid two-phase system was developed for the chiral separation of racemic phenylalanine with new dication imidazolium-based chiral ionic liquids. Preliminary experiments showed distinct enantioselectivity in amino acid extraction with the novel solid-liquid two-phase system, more L-enantiomer of amino acid cooperatively interacted with ionic liquids and copper ions to be the solid phase. Various factors, including the alkyl chain length of cations of ionic liquids, the amount of copper acetate, the ratio of n(ILs)/n(Cu(2+)), the amount of water and racemic phenylalanine, the resolution time together with the resolution temperature, were systematically investigated for their influence on resolution efficiency. The results showed that, under a certain condition, the enantiomeric excess value and the yield of phenylalanine in liquid phase (mainly containing D-enantiomer) were 67.8% and 96.5%, the enantiomeric excess value and the yield of phenylalanine in solid phase (mainly containing L-enantiomer) were 99.2% and 85.2%. Finally, 2D NMR technology, infrared spectroscopy and molecular simulation method were used to study the interaction mechanism. The results indicated that L-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+). The novel system has characteristics of free-organic solvent, simple operation, fast separation process and very high resolution efficiency for racemic phenylalanine. This work could provide a new and alternative resolution approach for other chiral separations.

  4. Non-racemic Amino Acid Production by Ultraviolet Irradiation of Achiral Interstellar Ice Analogs with Circularly Polarized Light

    Science.gov (United States)

    de Marcellus, Pierre; Meinert, Cornelia; Nuevo, Michel; Filippi, Jean-Jacques; Danger, Grégoire; Deboffle, Dominique; Nahon, Laurent; Le Sergeant d'Hendecourt, Louis; Meierhenrich, Uwe J.

    2011-02-01

    The delivery of organic matter to the primitive Earth via comets and meteorites has long been hypothesized to be an important source for prebiotic compounds such as amino acids or their chemical precursors that contributed to the development of prebiotic chemistry leading, on Earth, to the emergence of life. Photochemistry of inter/circumstellar ices around protostellar objects is a potential process leading to complex organic species, although difficult to establish from limited infrared observations only. Here we report the first abiotic cosmic ice simulation experiments that produce species with enantiomeric excesses (e.e.'s). Circularly polarized ultraviolet light (UV-CPL) from a synchrotron source induces asymmetric photochemistry on initially achiral inter/circumstellar ice analogs. Enantioselective multidimensional gas chromatography measurements show significant e.e.'s of up to 1.34% for (13C)-alanine, for which the signs and absolute values are related to the helicity and number of CPL photons per deposited molecule. This result, directly comparable with some L excesses measured in meteorites, supports a scenario in which exogenous delivery of organics displaying a slight L excess, produced in an extraterrestrial environment by an asymmetric astrophysical process, is at the origin of biomolecular asymmetry on Earth. As a consequence, a fraction of the meteoritic organic material consisting of non-racemic compounds may well have been formed outside the solar system. Finally, following this hypothesis, we support the idea that the protosolar nebula has indeed been formed in a region of massive star formation, regions where UV-CPL of the same helicity is actually observed over large spatial areas.

  5. Magnetic resonance imaging of racemous cysticercosis of the cauda equina; Ressonancia magnetica de paciente com cisticercose racemosa da cauda equina

    Energy Technology Data Exchange (ETDEWEB)

    Costa Junior, Leodante Batista da; Lemos, Sandro Pedroso [Hospital da Baleia, Belo Horizonte, MG (Brazil). Servico de Neurocirurgia; Lambertucci, Jose Roberto [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Faculdade de Medicina. Servico de Doencas Infecciosas e Parasitarias

    2003-12-01

    37-year-old man presented with low back pain for the last 6 months followed by sensation of numbness in the lower limbs that evolved with paraparesis, urinary retention and impotence. Subsequently, he lost control over the bowel function. Neurological examination revealed increased muscle tone along with grade zero power in both lower limbs. Knee and ankle jerks were exaggerated. Nine months prior to admission, a type II diabetes mellitus was diagnosed and he has been taking insulin ever since. MRI revealed multiple cystic lesions in the cauda equina opposite the L1-S1 vertebral bodies with no involvement of the spinal cord (Figure A: sagittal section T1-weighted image after contrast with cystic lesions on the left side - yellow arrow -, and T2-weighted image on the right - red arrows pointing cystic lesions). The cysts were hypointense on T1-weighted images (Figure B: horizontal section - yellow arrows) and hyperintense in T2-weighted images (Figure A - red arrows). Computerized tomography of the brain showed moderate ventricle dilatation (Figure C) with no intra or extra axial lesions. He was submitted to laminectomy and the cysts were surgically removed. An intense inflammatory process (arachnoiditis) involving the nerve roots of the cauda equina was reported. Histology of the surgical specimen confirmed the diagnosis of racemous cysticercosis. He improved quickly after surgery. Three months later, at the outpatient clinic, he walked with support, resumed sphincter control of the bladder and bowel and had no more pain. Ten months later he returned to hospital walking with crutches, with hypoesthesia and paraesthesia on the left leg and urinary incontinence. He refused treatment with albendazole and steroids. (author)

  6. Aspartic Acid Racemization and Collagen Degradation Markers Reveal an Accumulation of Damage in Tendon Collagen That Is Enhanced with Aging*

    Science.gov (United States)

    Thorpe, Chavaunne T.; Streeter, Ian; Pinchbeck, Gina L.; Goodship, Allen E.; Clegg, Peter D.; Birch, Helen L.

    2010-01-01

    Little is known about the rate at which protein turnover occurs in living tendon and whether the rate differs between tendons with different physiological roles. In this study, we have quantified the racemization of aspartic acid to calculate the age of the collagenous and non-collagenous components of the high strain injury-prone superficial digital flexor tendon (SDFT) and low strain rarely injured common digital extensor tendon (CDET) in a group of horses with a wide age range. In addition, the turnover of collagen was assessed indirectly by measuring the levels of collagen degradation markers (collagenase-generated neoepitope and cross-linked telopeptide of type I collagen). The fractional increase in d-Asp was similar (p = 0.7) in the SDFT (5.87 × 10−4/year) and CDET (5.82 × 10−4/year) tissue, and d/l-Asp ratios showed a good correlation with pentosidine levels. We calculated a mean (±S.E.) collagen half-life of 197.53 (±18.23) years for the SDFT, which increased significantly with horse age (p = 0.03) and was significantly (p < 0.001) higher than that for the CDET (34.03 (±3.39) years). Using similar calculations, the half-life of non-collagenous protein was 2.18 (±0.41) years in the SDFT and was significantly (p = 0.04) lower than the value of 3.51 (±0.51) years for the CDET. Collagen degradation markers were higher in the CDET and suggested an accumulation of partially degraded collagen within the matrix with aging in the SDFT. We propose that increased susceptibility to injury in older individuals results from an inability to remove partially degraded collagen from the matrix leading to reduced mechanical competence. PMID:20308077

  7. Identification of isomerization and racemization of aspartate in the Asp-Asp motifs of a therapeutic protein.

    Science.gov (United States)

    Zhang, Jennifer; Yip, Holly; Katta, Viswanatham

    2011-03-15

    A thermally stressed Fab molecule showed a significant increase of basic variants in imaged capillary isoelectric focusing (iCIEF) analysis. Mass analyses of the reduced protein found an increase in -18Da species from both light chain and heavy chain. A tryptic peptide map identified two isoAsp-containing peptides, both containing Asp-Asp motifs and located in complementarity-determining regions (CDRs) of light chains and heavy chains, respectively. The approaches of hydrolyzing succinimide in H(2)(18)O followed by tryptic digestion were used to label and identify the sites of isomerization. This method enabled identification of the isomerization site by comparing the MS/MS spectra of isomerized peptides with and without (18)O incorporation. The light chain peptide L2 VTITCITSTDID(12)DDMNWYQQKPGK underwent simultaneous isomerization and recemization at residue Asp-12 after thermal stress as evidenced by the coinjection of synthetic peptide L2 with l-Asp-12, l-isoAsp-12, d-Asp-12, and d-isoAsp-12, respectively. A thermal stress study of the synthetic peptide (l-)L2 showed that the isomerization and racemization did not occur, indicating that the Asp degradation in this Asp-Asp motif is more related to the protein conformation than the primary sequence. Another isomerization site was identified as Asp-24 in the heavy chain peptide H5 QAPGQGLEWMGWINTYTGETTYAD(24)DFK. No other isomerizations were detected in CDR peptides containing either Asp-Ser or Asp-Thr motifs. Copyright © 2010 Elsevier Inc. All rights reserved.

  8. Stereoselective pharmacokinetic analysis of tramadol and its main phase I metabolites in healthy subjects after intravenous and oral administration of racemic tramadol.

    Science.gov (United States)

    García Quetglas, Emilio; Azanza, Jose Ramón; Cardenas, Ernesto; Sádaba, Belén; Campanero, Miguel Angel

    2007-01-01

    The kinetics of tramadol enantiomers are stereoselective when doses of the racemic drug are given orally. To document whether the route of administration determines the stereoselective kinetics of tramadol enantiomers, healthy volunteers received 100 mg oral or intravenous doses of racemic tramadol, and serial blood samples were obtained to assay tramadol enantiomers and their main phase I metabolites, O-demethyltramadol and N-demethyltramadol. To assess accurately the involvement of their metabolites in the pharmacokinetics of tramadol, it is essential to determine the rate and extent of the formation of the enantiomers of these metabolites. A simultaneous pharmacokinetic model describing the plasma concentration-curves of the generated metabolites and the parent compounds after intravenous and oral drug administration is developed and presented. Tramadol and O-demethyltramadol were the major compounds detected in plasma after intravenous administration. Nevertheless, the N-demethylation of tramadol showed a significant increase when the oral route was used. After both oral and intravenous doses, the kinetics of the tramadol enantiomers were stereoselective. The AUC for (R )-(+)-tramadol was greater than the AUC for (S)-(-)-tramadol. The formation of N-demethyltramadol also was enantioselective after oral administration of racemic tramadol, with a greater AUC for (R)-(+)-N-demethyltramadol than for (S)-(-)-N-demethyltramadol. In the opposite form, (S)-(-)-O-demethyltramadol was formed faster than (R)-(+)-O-demethyltramadol. The metabolism of tramadol was also route-dependent with a different enantiomeric ratio for tramadol and its main phase I metabolites after intravenous and oral administration. The disposition of N-demethyltramadol was concentration-dependent.

  9. Racemic synthesis and solid phase peptide synthesis application of the chimeric valine/leucine derivative 2-amino-3,3,4-trimethyl-pentanoic acid.

    Science.gov (United States)

    Pelà, M; Del Zoppo, L; Allegri, L; Marzola, E; Ruzza, C; Calo, G; Perissutti, E; Frecentese, F; Salvadori, S; Guerrini, R

    2014-07-01

    The synthesis of non natural amino acid 2-amino-3,3,4-trimethyl-pentanoic acid (Ipv) ready for solid phase peptide synthesis has been developed. Copper (I) chloride Michael addition, followed by a Curtius rearrangement are the key steps for the lpv synthesis. The racemic valine/leucine chimeric amino acid was then successfully inserted in position 5 of neuropeptide S (NPS) and the diastereomeric mixture separated by reverse phase HPLC. The two diastereomeric NPS derivatives were tested for intracellular calcium mobilization using HEK293 cells stably expressing the mouse NPS receptor where they behaved as partial agonist and pure antagonist.

  10. Comparative Optical Separation of Racemic Ibuprofen by Using Chiral Stationary Phase%运用手性固定相研究外消旋布洛芬的光学分离

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Ibuprofen is widely used as a non-steroidal anti-inflammatory drug and produced as racemic mixture. Its pharmacological activity resides only in S-(+)-enantiomer, and R-(-)-enantiomer is not only inactive but also has many side effects. Thus it is necessary to separate Renanfiomer from racemic ibuprofen. We studied optical separation of racemic Ibuprofen with chiral high performance liquid chromatography (HPLC). Out of three different chiral stationary phases, which were selected on the basis of structure and availability, two were found to be effective. There was optimum eluent composition for each stationary phase for good resolution in optical separation. Resolution decreased with increase of eluent flow rate, but effect of injection volume on resolution was insignificant at high eluent flow rate.

  11. Cocrystallizing natural RNA with its unnatural mirror image: biochemical and preliminary X-ray diffraction analysis of a 5S rRNA A-helix racemate

    Energy Technology Data Exchange (ETDEWEB)

    Förster, Charlotte; Brauer, Arnd B. E.; Lehmann, Daniel; Borowski, Tordis; Brode, Svenja; Fürste, Jens P. [Institute of Chemistry and Biochemistry, Free University Berlin, Thielallee 63, 14195 Berlin (Germany); Perbandt, Markus; Betzel, Christian [Institute of Biochemistry and Molecular Biology, University of Hamburg, c/o DESY, Notkestrasse 85, Building 22a, 22603 Hamburg (Germany); Erdmann, Volker A., E-mail: erdmann@chemie.fu-berlin.de [Institute of Chemistry and Biochemistry, Free University Berlin, Thielallee 63, 14195 Berlin (Germany)

    2007-10-01

    A 5S rRNA A-helix 7-mer oligonucleotide was chemically synthesized both as d-RNA and as l-RNA, biochemically investigated, crystallized as a stochiometric racemate and examined by X-ray diffraction. Chemically synthesized RNAs with the unnatural l-configuration possess enhanced in vivo stability and nuclease resistance, which is a highly desirable property for pharmacological applications. For a structural comparison, both l- and d-RNA oligonucleotides of a shortened Thermus flavus 5S rRNA A-helix were chemically synthesized. The enantiomeric RNA duplexes were stochiometrically cocrystallized as a racemate, which enabled analysis of the d- and l-RNA enantiomers in the same crystals. In addition to a biochemical investigation, diffraction data were collected to 3.0 Å resolution using synchrotron radiation. The crystals belonged to space group P3{sub 1}21, with unit-cell parameters a = b = 35.59, c = 135.30 Å, γ = 120° and two molecules per asymmetric unit.

  12. Organocatalytic aza-Michael/retro-aza-Michael reaction: pronounced chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction.

    Science.gov (United States)

    Cai, Yong-Feng; Li, Li; Luo, Meng-Xian; Yang, Ke-Fang; Lai, Guo-Qiao; Jiang, Jian-Xiong; Xu, Li-Wen

    2011-05-01

    A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions.

  13. Quantum-chemical analysis of thermodynamics of two-dimensional cluster formation of racemic α-amino acids at the air/water interface.

    Science.gov (United States)

    Vysotsky, Yu B; Fomina, E S; Belyaeva, E A; Aksenenko, E V; Fainerman, V B; Vollhardt, D; Miller, R

    2011-03-17

    The quantum-chemical semiempiric PM3 method is used to calculate the thermodynamic parameters of clusterization for the racemic α-amino acids C(n)H(2n+1)CHNH(2)COOH with n=5-15 at 278 and 298 K. Possible relative orientations of the monomers in the heterochiral clusters are considered. It is shown that, for the racemic mixtures of α-amino acids, the formation of heterochiral 2D films is most energetically preferable with the alternating (rather than "checkered") packing of the enantiomers with opposite specific rotation. The two enantiomeric forms of α-amino acids in the heterochiral 2D clusters are tilted with respect to the normal to the q direction at angles of φ(1)=20° and φ(2) = 33°, whereas the single enantiomeric forms are oriented at an angle of δ=9° with respect to the normal to the p direction. It is shown that the heterochiral 2D film based on the α-amino acid structures oriented at the angle φ(2)=33° with respect to the normal to the q direction possesses a rectangular unit cell with the geometric parameters a = 4.62 Å and b = 10.70 Å and the tilt angle of the alkyl chain of the molecule with respect to the interface t(2)=35°, which is in good agreement with the X-ray structural data a=4.80 Å, b=9.67 Å, and t(2)=37°. The parameters of the lattice structure of monolayers formed by amphiphilic amino acids are shown to be determined by the "a" type of the intermolecular H-H interactions, whereas the tilt angle of the molecules with respect to the interface depends on the volume and the structure of the functional groups involved in the hydrophilic part of the molecule. Spontaneous clusterization of the racemic form of α-amino acids at the air/water interface at 278 K takes place if the alkyl chain length is equal or higher than 12-13 carbon atoms, whereas for 298 K this clusterization threshold corresponds to 14 carbon atoms in the hydrocarbon chain. These values agree with the experimental data. © 2011 American Chemical Society

  14. Efficient resolution of (±)-rans-2,3-diphenylpiperazine using (1)-(+)-10-camphorsulfonic acid and enrichment of enantiomeric purity of non-racemic 2,3-diphenylpiperazine using different achiral acids

    Indian Academy of Sciences (India)

    Pothiappan Vairaprakash; Mariappan Periasamy

    2008-01-01

    Enantiomerically pure (,)-(+)-2,3-diphenylpiperazine with 98% was obtained by resolution of the corresponding racemic mixture using (1)-(+)-10-camphorsulfonic acid. The partially resolved enriched sample of (,)-(-)-2,3-diphenylpiperazine with 73% ee was purified to obtain samples of 97% ee using different achiral acids via the preparation of either homochiral or heterochiral hydrogen bonded aggregates.

  15. Optical Separation of Racemic Phenyl-alanine,and Structure of Complex Consisting of R-Phenylalanine and R-Mandelic Acid

    Institute of Scientific and Technical Information of China (English)

    胡自强; 徐端钧; 徐元植; 吴景云; 蒋燕南

    2004-01-01

    The racemic phenylalanine has been separated by (R)-mandelic acid through the formation of diastereomeric molecular complex. The crystal of the title chiral complex (C8H8O3·C9H11NO2, Mr = 317.33) belongs to monoclinic, space group C2 with a = 19.391(3), b = 5.715(4), c = 15.755(3)A,β= 115.23(1)°, V = 1579(1) A3, Z = 4, Dc = 1.335 g/cm3, F(000) = 672, μ= 0.099 mm-1, R = 0.033 and Wr = 0.060 for 1278 observed reflections (I > 2σ(I)). The complex consists of (R)-mandelic acid and (R)-phenylalanine in 1:1 molar ratio, and the complex molecules form layered crystal structure by self-assembly through intermolecular H-bonding between carboxyl and carboxylate of the neighboring molecules.

  16. Racemization Energy of 3,2'-Tetramethylene-2-phenyl-6-(pyrid-2''-yl)pyridine Estimated by Temperature Variation {sup 1}H NMR Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Motiur Rahman, A. F. M. [King Saud Univ., Riyadh (Saudi Arabia); Cha, Hyochang; Kwak, Kyungsook; Lee, Eungseok; Jahng, Yurngdong [Yeungnam Univ., Gyeongsan (Korea, Republic of)

    2013-02-15

    In conclusion, the racemization energy for the two conformational enantiomers of 3,2'-tetramethylene-2-phenyl-6-(pyrid-2''-yl)pyridine was estimated by temperature variation {sup 1}H NMR method to give 23 kcal/mole. Studies on the conformation of annulated bi-aryls have long been pursued extensively due to interest in the chirality and spectroscopic properties of conformationally restricted bi-aryls and their possible use in the determination of the absolute configuration of atropisomeric biaryls. One of the most extensively studied systems is 2,2'-polymethylenebi-phenyls (1), of which the chirality depends on the biphenyl unit as the stereogenic element.

  17. Cytotoxic activity of new racemic and optically active N-phosphonoalkyl bicyclic β-amino acids against human malignant cell lines.

    Science.gov (United States)

    Todorov, Petar T; Wesselinova, Diana W; Pavlov, Nikola D; Martinez, Jean; Calmes, Monique; Naydenova, Emilia D

    2012-10-01

    The cytotoxic effects of novel racemic and optically active constrained N-phosphonoalkyl bicyclic β-amino acids were tested against a panel of human tumor cell lines. All of the compounds investigated exhibited different concentration-dependent antiproliferative effects against the HT-29, MDA-MB-231, HepG2 and HeLa cell lines after 24 h treatment. The most sensitive cells were the HeLa cells at various concentrations of the four compounds tested. The aminophosphonate 3 exerted the most pronounced antiproliferative effect against the HeLa cells (inhibition of the cell vitality up to 70% at 0.5 mg/ml) and was not toxic to the normal Lep3 cells at lower concentration. Furthermore, the N-phosphonophenyl derivatives 1 and 2 displayed antiproliferative effect against mainly the MDA-MB-231 tumour cells at higher concentration.

  18. Crystallization of Enantiomerically Pure Proteins from Quasi-Racemic Mixtures: Structure Determination by X-Ray Diffraction of Isotope-Labeled Ester Insulin and Human Insulin.

    Science.gov (United States)

    Mandal, Kalyaneswar; Dhayalan, Balamurugan; Avital-Shmilovici, Michal; Tokmakoff, Andrei; Kent, Stephen B H

    2016-03-01

    As a part of a program aimed towards the study of the dynamics of human insulin-protein dimer formation using two-dimensional infrared spectroscopy, we used total chemical synthesis to prepare stable isotope labeled [(1-(13) C=(18) O)Phe(B24) )] human insulin, via [(1-(13) C=(18) O)Phe(B24) )] ester insulin as a key intermediate product that facilitates folding of the synthetic protein molecule (see preceding article). Here, we describe the crystal structure of the synthetic isotope-labeled ester insulin intermediate and the product synthetic human insulin. Additionally, we present our observations on hexamer formation with these two proteins in the absence of phenol derivatives and/or Zn metal ions. We also describe and discuss the fractional crystallization of quasi-racemic protein mixtures containing each of these two synthetic proteins.

  19. HPLC enantioseparation of racemic bupropion, baclofen and etodolac: modification of conventional ligand exchange approach by pre-column formation of chiral ligand exchange complexes.

    Science.gov (United States)

    Singh, Manisha; Bhushan, Ravi

    2016-11-01

    Separation of racemic mixture of (RS)-bupropion, (RS)-baclofen and (RS)-etodolac, commonly marketed racemic drugs, has been achieved by modifying the conventional ligand exchange approach. The Cu(II) complexes were first prepared with a few l-amino acids, namely, l-proline, l-histidine, l-phenylalanine and l-tryptophan, and to these was introduced a mixture of the enantiomer pair of (RS)-bupropion, or (RS)-baclofen or (RS)-etodolac. As a result, formation of a pair of diastereomeric complexes occurred by 'chiral ligand exchange' via the competition between the chelating l-amino acid and each of the two enantiomers from a given pair. The diastereomeric mixture formed in the pre-column process was loaded onto HPLC column. Thus, both the phases during chromatographic separation process were achiral (i.e. neither the stationary phase had any chiral structural feature of its own nor did the mobile phase have any chiral additive). Separation of diastereomers was successful using a C18 column and a binary mixture of MeCN and TEAP buffer of pH 4.0 (60:40, v/v) as mobile phase at a flow rate of 1 mL/min and UV detection at 230 nm for (RS)-Bup, 220 nm for (RS)-Bac and 223 nm for (RS)-Etd. Baseline separation of the two enantiomers was obtained with a resolution of 6.63 in <15 min. Copyright © 2016 John Wiley & Sons, Ltd.

  20. Scandium versus yttrium{amino-alkoxy-bis(phenolate)} complexes for the stereoselective ring-opening polymerization of racemic lactide and β-butyrolactone.

    Science.gov (United States)

    Chapurina, Yulia; Klitzke, Joice; Casagrande, Osvaldo de L; Awada, Mouhamad; Dorcet, Vincent; Kirillov, Evgueni; Carpentier, Jean-François

    2014-10-14

    Scandium and yttrium amide complexes Ln{ONXO(R1,R2)}(N(SiHMe2)2)(THF)n (Ln = Sc, n = 0 or Y, n = 1; X = NMe2 or OMe; R(1) = Cumyl or p-Cl-Cumyl; R(2) = Me or Cumyl) were prepared by aminolysis of Ln[N(SiHMe2)2]3(THF) with the corresponding tetradentate diamino- or alkoxy-amino-bis(phenol) pro-ligands {ONXO(R1,R2)}H2. In the solid state and in toluene solution, the scandium complexes are monomeric and 5-coordinated, while the analogous yttrium complexes all bear an extra THF-coordinated molecule and are 6-coordinated. Sc{ONXO(R1,R2)}(N(SiHMe2)2) complexes are single-site initiators for the ring-opening polymerization (ROP) of racemic lactide but are less active than their yttrium analogues Y{ONXO(R1,R2)}(N(SiHMe2)2)(THF); also, in contrast to the latter ones, they are inactive in the ROP of the more demanding racemic β-butyrolactone. On the other hand, the scandium amide complexes feature a significantly improved control over the ROP of lactide, yielding PLAs with much narrower molecular weight distributions (Đ(M) < 1.1 for Sc vs. 1.5-2.0 for Y). The yttrium complex with the very bulky o,p-dicumyl-substituted ligand is more heteroselective than its scandium analogue (P(r) = 0.88 vs. 0.83), while the opposite is observed with complexes based on p-methyl-substituted ligands (P(r) = 0.50 in toluene or 0.72-0.75 in THF for Y vs. P(r) = 0.75-0.83 for Sc in toluene). These reactivity and selectivity trends are rationalized by a much more sterically crowded coordination sphere in scandium than in yttrium complexes.

  1. Repetibilidade e número mínimo de medições para caracteres de cacho de bacabi (Oenocarpus mapora Repeatability and minimum number of measurements for characters of bacabi palm (Oenocarpus mapora racemes

    Directory of Open Access Journals (Sweden)

    Maria do Socorro Padilha de Oliveira

    2010-12-01

    Full Text Available A bacabi (Oenocarpus mapora H. Karsten é uma palmeira perene nativa da Amazônia, que produz cachos com centenas de frutos que apresentam grande potencialidade à agroindústria de polpa, mas tem sido pouco estudada. Os objetivos deste trabalho foram estimar os coeficientes de repetibilidade e determinar a previsibilidade e o número de medições necessárias para caracteres de cacho dessa palmeira. Foram avaliados 27 indivíduos de bacabi pertencentes ao Banco de Germoplasma de Oenocarpus/Jessenia da Embrapa Amazônia Oriental, em Belém-PA. De cada planta, foram colhidos três cachos em maturação completa para a mensuração de seis caracteres: peso total do cacho (PTC e de frutos por cacho (PFC, número de ráquilas por cacho (NRC, comprimento da ráquis por cacho (CRC, peso de 100 frutos (PCF e rendimento de frutos por cacho (RFC. As estimativas de repetibilidade foram obtidas pelos métodos estatísticos da análise de variância, componentes principais e análise estrutural. Em todos os caracteres, as estimativas de repetibilidade apresentaram valores muito semelhantes nos três métodos. As estimativas dos coeficientes de repetibilidade e as previsibilidades foram relativamente altas (r 0,60 e R² 81,7% para os caracteres número de ráquilas e rendimento de frutos por cacho, demonstrando regularidade dos genótipos nas várias medições (cachos, em todos os métodos. Para esses caracteres, o número mínimo de cachos necessários para a avaliação do real valor dos genótipos foi de treze (RFC e cinco (NRC cachos com confiabilidade de 95%, tornando-os factíveis no uso de inferências genéticas para as condições do estudo. Os demais caracteres exibiram repetibilidades e coeficientes de determinação de médias a baixas magnitudes, indicando necessidade de maior controle ambiental para suas mensurações.Bacabi (Oenocarpus mapora H. Karsten is a native Amazonian palm that produces racemes with hundreds of fruits with great

  2. Penicillium expansum脂肪酶选择性拆分外消旋萘普生%Enantioselective Resolution of Racemic Naproxen by a Lipase from Penicillium expansum

    Institute of Scientific and Technical Information of China (English)

    唐良华; 蔡志雄; 苏敏; 祝铃; 周琼; 吕博彦

    2011-01-01

    为了实现同定化扩展青霉TS414(Penicillium expansum TS414)脂肪酶在有机相中对外消旋萘普生的高效拆分,实验考察了水分、温度、有机溶剂、酶浓度、醇结构和醇浓度对酶促拆分反应的影响,确立了优化的酯化反应条件为:异辛烷为溶剂,外消旋荼普生2.15 mmol/L,正丙醇34.3 mmol/L,固定化酶量12g/L,水0.05%(φ),40℃恒温摇床中200 r/min反应100 h.在此条件下,酯化拆分反应的转化率为48.3%.结果表明,固定化Penicillium expansum脂肪酶是一种较为理想的用于外消旋萘普生拆分的工具酶.%In order to resolute racemic naproxen with high efficiency by the immobilized Penicilllum expansum TS414 lipase in organic solvent, the factors affecting the resolution of (R, S)-naproxen by lipase-catalyzed esterification reaction were investigated, including water concentration, temperature, organic solvent, enzyme concentration, structure and concentration of alcohol. And experiments were designed to optimize the conditions of esterification reaction. Under the optimal condition (isooctane as solvent, 2.15 mmol/L ibuprofen, 12 g/L lipase, 34.3 mmol/L 1-propanol, 0.05%(p) water, 200 r/min, 40 °C for 100 h), the conversion rate could reach 48.3%. Thus, Penicillium expansum TS414 lipase could be used as a perfect tool enzyme with high enantioselectivity and had a great potential for commercial applications in the resolution of racemic naproxen and other non-steroidal anti-inflammatory drugs of 2-aryl propionic Acids.

  3. Racemic Salsolinol and its Enantiomers Act as Agonists of the μ-Opioid Receptor by Activating the Gi Protein-Adenylate Cyclase Pathway

    Science.gov (United States)

    Berríos-Cárcamo, Pablo; Quintanilla, María E.; Herrera-Marschitz, Mario; Vasiliou, Vasilis; Zapata-Torres, Gerald; Rivera-Meza, Mario

    2017-01-01

    Background: Several studies have shown that the ethanol-derived metabolite salsolinol (SAL) can activate the mesolimbic system, suggesting that SAL is the active molecule mediating the rewarding effects of ethanol. In vitro and in vivo studies suggest that SAL exerts its action on neuron excitability through a mechanism involving opioid neurotransmission. However, there is no direct pharmacologic evidence showing that SAL activates opioid receptors. Methods: The ability of racemic (R/S)-SAL, and its stereoisomers (R)-SAL and (S)-SAL, to activate the μ-opioid receptor was tested in cell-based (light-emitting) receptor assays. To further characterizing the interaction of SAL stereoisomers with the μ-opioid receptor, a molecular docking study was performed using the crystal structure of the μ-opioid receptor. Results: This study shows that SAL activates the μ-opioid receptor by the classical G protein-adenylate cyclase pathway with an half-maximal effective concentration (EC50) of 2 × 10−5 M. The agonist action of SAL was fully blocked by the μ-opioid antagonist naltrexone. The EC50 for the purified stereoisomers (R)-SAL and (S)-SAL were 6 × 10−4 M and 9 × 10−6 M respectively. It was found that the action of racemic SAL on the μ-opioid receptor did not promote the recruitment of β-arrestin. Molecular docking studies showed that the interaction of (R)- and (S)-SAL with the μ-opioid receptor is similar to that predicted for the agonist morphine. Conclusions: It is shown that (R)-SAL and (S)-SAL are agonists of the μ-opioid receptor. (S)-SAL is a more potent agonist than the (R)-SAL stereoisomer. In silico analysis predicts a morphine-like interaction between (R)- and (S)-SAL with the μ-opioid receptor. These results suggest that an opioid action of SAL or its enantiomers is involved in the rewarding effects of ethanol. PMID:28167903

  4. Simple and Efficient Synthesis of Racemic 2-(tert-Butoxycarbon-ylamino-2-methyl-3-(1H-1,2,4-triazol-1-ylpropanoic Acid, a New Derivative of β-(1,2,4-Triazol-1-ylalanine

    Directory of Open Access Journals (Sweden)

    Abdelali Kerbal

    2011-04-01

    Full Text Available A simple synthetic approach to racemic N-tert-butyloxycarbonyl-2-methyl-3-(1H-1,2,4-triazol-1-ylalanine (5 in four steps and 68% overall yield starting from oxazoline derivative 1 is reported. This synthesis involves the alkylation of 1H-1,2,4-triazole with an O-tosyloxazoline derivative, followed by an oxazoline ring-opening reaction and oxidation of the N-protected β‑aminoalcohol by potassium permanganate.

  5. Biomarkers in sediments. The racemization/epiremitation of amino acids like tool in geochronology and paleothermometrics; Estratigrafia biomolecular. La racemizacion/epimerizacion de aminoacidos como herramienta geocronologica y paleotermometrica

    Energy Technology Data Exchange (ETDEWEB)

    Torres, T.; Llamas, F. J.; Canoira, L.; Garcia-Alonso, P.; Ortiz, J. E. [Universidad Politecnica de Madrid (Spain)

    1999-07-01

    The study of amino acids as biomarkers in sediments has become a necessary methodology and tool for the analysis of palaeoenvironmental conditions and, therefore, of climatic evolution in the past. Research based on the selection and analysis of geological biomarkers, and more specifically activities relating to the racemization/epimerization of amino acids, makes it possible to obtain the geochronological and photoelectrochemical data required to establish different hypotheses for Long-Term Performance Assessment of a repository for high level radioactive wastes. (Author)

  6. Preparation of Optically Active Alkoxy-serines from Amino-amide Racemate Catalyzed by Escherichia coil Cells with Peptidase B Activity

    Institute of Scientific and Technical Information of China (English)

    WANG Zhi-yuan; LIU Jun-zhong; XU Li-sheng; ZHANG Hong-juan; LIU Qian; JIAO Qing-cai

    2013-01-01

    Alkoxy-L-serines are useful for peptide syntheses.The demand for alkoxy-L-serines in the pharmaceutical industries continues to increase because of their multiple physiological effects.In this research,an improved method for alkoxy-L-serines synthesis is reported.A series of substrates,DL-β-alkoxy-α-amino propionamides,was used for the synthesis of alkoxy-serines catalyzed by Escherichia coli cells with peptidase B(PepB) activity.The results show that PepB has a high resolution activity with DL-β-alkoxy-α-amino propionamides as substrate.Reaction conditions were optimized,i.e.,DL-β-methoxy-α-amino propionamide as substrate at pH=9.0,40 ℃ and 14 h,and the optimal reaction concentration is 400 mmol/L.The results also show that divalent metal cations exhibit different effects on the PepB activity,for example,Zn2+ and Cu2+ can obviously inhibit the activity of PepB,whereas Co2+,Ca2+,Mn2+ and Mg2+ at low concentrations can activate PepB.This research provides access to enantiomerically enriched and valuable alkoxy-L-serines from a simple amino-amide racemate.

  7. Ultra-broad polypyrrole (PPy) nano-ribbons seeded by racemic surfactants aggregates and their high-performance electromagnetic radiation elimination

    Science.gov (United States)

    Jiao, Yingzhi; Wu, Fan; Zhang, Kun; Sun, Mengxiao; Xie, Aming; Dong, Wei

    2017-08-01

    Ribbon-like nano-structures possess high aspect ratios, and thus have great potential in the development of high-performance microwave absorption (MA) materials that can effectively eliminate adverse electromagnetic radiation. However, these nano-structures have been scarcely constructed in the field of MA, because of the lack of efficient synthetic routes. Herein, we developed an efficient method to successfully construct polypyrrole (PPy) nano-ribbons using the self-assembly aggregates of a racemic surfactant as the seeds. The frequency range with a reflection loss value of lower than -10 dB reached 7.68 GHz in the frequency range of 10.32-18.00 GHz, and surpassed all the currently reported PPy nano-structures, as well as most other MA nano-materials. Through changing the amount of surfactant, both the nano-structures and MA performance can be effectively regulated. Furthermore, the reason behind the high-performance MA of PPy nano-ribbons has been deeply explored. It opens up the opportunity for the application of conducting polymer nano-ribbons as a lightweight and tunable high-performance MA material, especially in applications of special aircraft and flexible electronics.

  8. Conventional Chiralpak ID vs. capillary Chiralpak ID-3 amylose tris-(3-chlorophenylcarbamate)-based chiral stationary phase columns for the enantioselective HPLC separation of pharmaceutical racemates.

    Science.gov (United States)

    Ahmed, Marwa; Gwairgi, Marina; Ghanem, Ashraf

    2014-11-01

    A comparative enantioselective analysis using immobilized amylose tris-(3-chlorophenylcarbamate) as chiral stationary phase in conventional high-performance liquid chromatography (HPLC) with Chiralpak ID (4.6 mm ID × 250 mm, 5 µm silica gel) and micro-HPLC with Chiralpak ID-3 (0.30 mm ID × 150 mm, 3 µm silica gel) was conducted. Pharmaceutical racemates of 12 pharmacological classes, namely, α- and β-blockers, anti-inflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs, and antiarrhythmic drugs were screened under normal phase conditions. The effect of an organic modifier on the analyte retentions and enantiomer recognition was investigated. Baseline separation was achieved for 1-acenaphthenol, carprofen, celiprolol, cizolirtine carbinol, miconazole, tebuconazole, 4-hydroxy-3-methoxymandelic acid, 1-indanol, 1-(2-chlorophenyl)ethanol, 1-phenyl-2-propanol, flavanone, 6-hydroxyflavanone, 4-bromogluthethimide, and pentobarbital on the 4.6 mm ID packed with a 5 µm silica column using conventional HPLC. Nonetheless, baseline separation was achieved for aminoglutethimide, naftopidil, and thalidomide on the 0.3 mm ID packed with a 3 µm silica capillary column.

  9. Enzymatic dynamic kinetic resolution of racemic N-formyl- and N-carbamoyl-amino acids using immobilized L-N-carbamoylase and N-succinyl-amino acid racemase.

    Science.gov (United States)

    Soriano-Maldonado, Pablo; Las Heras-Vazquez, Francisco Javier; Clemente-Jimenez, Josefa María; Rodriguez-Vico, Felipe; Martínez-Rodríguez, Sergio

    2015-01-01

    Taking advantage of the catalytic promiscuity of L-carbamoylase from Geobacillus stearothermophilus CECT43 (BsLcar) and N-succinyl-amino acid racemase from Geobacillus kaustophilus CECT4264 (GkNSAAR), we have evaluated the production of different optically pure L-α-amino acids starting from different racemic N-formyl- and N-carbamoyl-amino acids using a dynamic kinetic resolution approach. The enzymes were immobilized on two different solid supports, resulting in improved stability of the enzymes in terms of thermostability and storage when compared to the enzymes in solution. The bienzymatic system retained up to 80% conversion efficiency after 20 weeks at 4 °C and up to 90% after 1 week at 45 °C. The immobilization process also resulted in a great enhancement of the activity of BsLcar toward N-formyl-tryptophan, showing for the first time that substrate specificity of L-carbamoylases can be influenced by this approach. The system was effective for the biosynthesis of natural and unnatural L-amino acids (enantiomeric excess (e.e.) >99.5%), such as L-methionine, L-alanine, L-tryptophan, L-homophenylalanine, L-aminobutyric acid, and L-norleucine, with a higher performance toward N-formyl-α-amino acid substrates. Biocatalyst reuse was studied, and after 10 reaction cycles, over 75% activity remained.

  10. An unusual (10,3)-a racemic twofold interpenetrating network assembled from isolable tris(cyclopentadienyl)manganate and cesocene building blocks.

    Science.gov (United States)

    Kheradmandan, Sohrab; Schmalle, Helmut W; Jacobsen, Heiko; Blacque, Olivier; Fox, Thomas; Berke, Heinz; Gross, Mathias; Decurtins, Silvio

    2002-06-03

    The syntheses and X-ray crystal structures of [([18]crown-6)2Cs](+)-[Cp3Mn]- (1), [([18]crown-6)2Cs](+)-[Cp'3Mn]- (2), [CsCp'] (3), [(CsCp')2-([18]crown-6)] (4), and Cs[MnCp3] (5), and the synthesis of Cs[MnCp'3] (6) are reported (Cp' = C5H4Me). The anions [Cp3Mn]- (1-) and [Cp'3Mn]- (2-) are characterized by eta 2 coordination of all three Cp or Cp' rings. Measurements of the magnetic susceptibilities chi M resulted in values of mu eff = 6.20 microB (300 K), mu eff = 6.33 microB (301 K), and mu eff = 5.83 microB (300 K) for 1, 2, and 5, respectively, which are indicative of high-spin d5-Mn2+ centers. Density functional calculations illustrate that the coordination mode of 1- is characteristic for its sextet electronic ground state. Compound 3 forms infinite chains of cesocene-type sandwiches in the solid state, which are broken up into small subunits by the addition of crown ether to form 4. Compound 5 is a rare example of a (10,3)-a racemic interpenetrating network that crystallizes in the orthorhombic space group Pbca.

  11. Highly regio-and stereo-selective copolymerization of CO2 with racemic propylene oxide catalyzed by unsymmetrical (S,S,S)-salenCo(Ⅲ) complexes

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A novel unsymmetrical (S,S,S)-salen ligand bearing a derived chiral-BINOL was synthesized by the reaction of the condensation product of (1S,2S)-1,2-diaminocyclohexane mono(hydrogen chloride) with 3-adamanyl-5-tert-butyl-2-hydroxybenzalde-hyde and 3-formoyl-2-hydroxy-2’-alkyloxy-1,1’-binaphthyl,which originated from (S)-1,1’-bi-2-naphthol via a four-step reaction.The cobalt complexes of this ligand,in conjunction with a nucleophilic cocatalyst,exhibited excellent activity in catalyzing asymmetric,regio-and stereo-selective copolymerization of CO2 and racemic propylene oxide.The highest record of kinetic resolution coefficient (Krel) was obtained with the use of binary catalyst system consisting of (S,S,S)-salenCo(III) complex 1c and bulky bis(triphenylphosphine)-iminium chloride (PPNCl).The resulting poly(propylene carbonate)s have more than 99% carbonate linkages and more than 98% head-to-tail content.

  12. Sediment accumulation, stratigraphic order, and the extent of time-averaging in lagoonal sediments: a comparison of 210Pb and 14C/amino acid racemization chronologies

    Science.gov (United States)

    Kosnik, Matthew A.; Hua, Quan; Kaufman, Darrell S.; Zawadzki, Atun

    2015-03-01

    Carbon-14 calibrated amino acid racemization (14C/AAR) data and lead-210 (210Pb) data are used to examine sediment accumulation rates, stratigraphic order, and the extent of time-averaging in sediments collected from the One Tree Reef lagoon (southern Great Barrier Reef, Australia). The top meter of lagoonal sediment preserves a stratigraphically ordered deposit spanning the last 600 yrs. Despite different assumptions, the 210Pb and 14C/AAR chronologies are remarkably similar indicating consistency in sedimentary processes across sediment grain sizes spanning more than three orders of magnitude (0.1-10 mm). Estimates of long-term sediment accumulation rates range from 2.2 to 1.2 mm yr-1. Molluscan time-averaging in the taphonomically active zone is 19 yrs, whereas below the depth of final burial (~15 cm), it is ~110 yrs/5 cm layer. While not a high-resolution paleontological record, this reef lagoon sediment is suitable for paleoecological studies spanning the period of Western colonization and development. This sedimentary deposit, and others like it, should be useful, albeit not ideal, for quantifying anthropogenic impacts on coral reef systems.

  13. Effectiveness of Iron Ethylenediamine-N,N'-bis(hydroxyphenylacetic) Acid (o,o-EDDHA/Fe(3+)) Formulations with Different Ratios of Meso and d,l-Racemic Isomers as Iron Fertilizers.

    Science.gov (United States)

    Alcañiz, Sara; Jordá, Juana D; Cerdán, Mar

    2017-01-18

    Two o,o-EDDHA/Fe(3+) formulations (meso, 93.5% w/w of meso isomer; and d,l-racemic, 91.3% w/w of d,l-racemic mixture) were prepared, and their efficacy to avoid or to relieve iron deficiency in Fe-sufficient and Fe-deficient tomato plants grown on hydroponic solution was compared with that of the current o,o-EDDHA/Fe(3+) formulations (50% of meso and d,l-racemic isomers). The effectiveness of the three o,o-EDDHA/Fe(3+) formulations was different depending on the iron nutritional status of plants. The three o,o-EDDHA/Fe(3+) formulations tested were effective in preventing iron chlorosis in healthy plants. However, the higher the meso concentration in the formulations, the higher the effectiveness in the recovery of iron chlorotic plants from iron deficiency. Accordingly, o,o-EDDHA/Fe(3+) formulations rich in meso isomer are recommended in hydroponic systems.

  14. Calibration of amino acid racemization (AAR) kinetics in United States mid-Atlantic Coastal Plain Quaternary mollusks using 87Sr/ 86Sr analyses: Evaluation of kinetic models and estimation of regional Late Pleistocene temperature history

    Science.gov (United States)

    Wehmiller, J. F.; Harris, W.B.; Boutin, B.S.; Farrell, K.M.

    2012-01-01

    The use of amino acid racemization (AAR) for estimating ages of Quaternary fossils usually requires a combination of kinetic and effective temperature modeling or independent age calibration of analyzed samples. Because of limited availability of calibration samples, age estimates are often based on model extrapolations from single calibration points over wide ranges of D/L values. Here we present paired AAR and 87Sr/ 86Sr results for Pleistocene mollusks from the North Carolina Coastal Plain, USA. 87Sr/ 86Sr age estimates, derived from the lookup table of McArthur et al. [McArthur, J.M., Howarth, R.J., Bailey, T.R., 2001. Strontium isotopic stratigraphy: LOWESS version 3: best fit to the marine Sr-isotopic curve for 0-509 Ma and accompanying Look-up table for deriving numerical age. Journal of Geology 109, 155-169], provide independent age calibration over the full range of amino acid D/L values, thereby allowing comparisons of alternative kinetic models for seven amino acids. The often-used parabolic kinetic model is found to be insufficient to explain the pattern of racemization, although the kinetic pathways for valine racemization and isoleucine epimerization can be closely approximated with this function. Logarithmic and power law regressions more accurately represent the racemization pathways for all amino acids. The reliability of a non-linear model for leucine racemization, developed and refined over the past 20 years, is confirmed by the 87Sr/ 86Sr age results. This age model indicates that the subsurface record (up to 80m thick) of the North Carolina Coastal Plain spans the entire Quaternary, back to ???2.5Ma. The calibrated kinetics derived from this age model yield an estimate of the effective temperature for the study region of 11??2??C., from which we estimate full glacial (Last Glacial Maximum - LGM) temperatures for the region on the order of 7-10??C cooler than present. These temperatures compare favorably with independent paleoclimate information

  15. REPETIBILIDADE DE CARACTERES DO CACHO DE AÇAIZEIRO NAS CONDIÇÕES DE BELÉM-PA REPEATIBILITY OF CHARACTERS OF THE RACEME OF AÇAI PALM AT BELÉM-PA

    Directory of Open Access Journals (Sweden)

    MARIA DO SOCORRO PADILHA DE OLIVEIRA

    2001-12-01

    Full Text Available Estimou-se o coeficiente de repetibilidade em caracteres do cacho de açaizeiro (Euterpe oleracea Mart. nas condições de Belém-PA, com o intuito de determinar a capacidade de eles expressarem a variabilidade genética dessa fruteira. Para tanto, foram colhidos quatro cachos por planta, todos apresentando completa maturação, em 30 genótipos pertencentes à Coleção de Germoplasma de Açaí da Embrapa Amazônia Oriental, onde foram mensurados seis caracteres: peso total do cacho (PTC, peso de frutos por cacho (PFC, número de frutos por cacho (NFC, número de ráquilas por cacho (NRC, peso médio do fruto (PMF e rendimento de frutos por cacho (RFC. A análise da repetibilidade, do número de medições necessárias e do coeficiente de determinação para cada caráter foi obtida através do método da análise de variância, utilizando o modelo com dois fatores de variação. Verificou-se que todos os caracteres apresentaram diferenças significativas entre genótipos, com o número de frutos, número de ráquilas e peso médio do fruto, evidenciando diferenças ao nível de 1% de probabilidade. Porém, o maior coeficiente de repetibilidade foi registrado para peso médio do fruto, enquanto os demais caracteres apresentaram valores inexpressivos. Essa variável teve, também, o maior coeficiente de determinação; entretanto, o número de repetições desejável para esse caráter deve ser quase o triplo do usado nesse estudo. Pelo fato de o coeficiente de repetibilidade expressar o valor máximo de herdabilidade, conclui-se que o PMF pode ser usado como parâmetro de seleção em métodos de melhoramento menos rigorosos.Was considered the repeatibility coefficient in characters of raceme in açai palm (Euterpe oleracea Mart. at Belém-PA with the intention of determining their capacity to express the genetic variability of that fruit bowl. For that were picked four racemes by plant, all presenting complete maturation, in 30 genotypes

  16. Recent Research Development in Resolution Kinetics of Racemic Menthol by Lipase%脂肪酶动力学拆分薄荷醇的研究进展

    Institute of Scientific and Technical Information of China (English)

    念保义; 黄志华; 罗菊香; 牛玉

    2011-01-01

    从脂肪酶拆分薄荷醇的转酯化、水解反应的工艺和影响因素等方面,分析了脂肪酶动力学拆分过程的转酯化和水解反应的催化路径与特点,指出了脂肪酶拆分薄荷醇的最佳路径和工艺选择.综述了近10年来脂肪酶拆分制备工业重要的手性香料l-薄荷醇的研究进展,特别综述了具有工业化前景的脂肪酶催化拆分和单元操作工艺的研究进展.同时展望了未来脂肪酶拆分薄荷醇的研究方向.%A condensed review of the potential offered by lipase for resolution of racemic menthols for the past 10 years is presented.Especially, recent applications of the lipase catalytic approach and industrialization of unit operation to the preparation of the most important flavor, l-menthol, are comprehensively covered by analyzing their processes of transesterification, hydrolysis reaction and influential factors. The potential industrial processes based on lipase-catalytie methods are discussed in the terms of their advantages over classical ones. The optimal pathway of resolution is achieved by analyzing resolving routes of menthol and alternative of acyl agent for transesterification of menthol. And a vista of the future investigations is opened up for new realms from macro-kinetics of menthol resolution for the industrial processes.

  17. Synthesis and evaluation of the racemate and individual enantiomers of C-11 labeled methylphenidate as radioligands for the presynaptic dopaminergic neuron

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Y.S.; Fowler, J.S.; Volkow, N.D. [Brookhaven National Lab., Upton, NY (United States)] [and others

    1994-05-01

    Methylphenidate (MP, ritalin) is a psychostimulant drug widely used to treat attention deficit hyperactivity disorder and narcolepsy. Its therapeutic properties are attributed to inhibition of the dopamine (DA) transporter enhancing synaptic DA. MP has two chiral centers and is marketed as the dl-threo racemic form. However, its pharmacological activity is believed due solely to the d-enantiomer. We have synthesized [{sup 11}C]d,l-threo-methylphenidate ([{sup 11}C]MP) in order to examine its pharmacokinetics in vivo and to examine its suitability as a radioligand for PET studies of the presynaptic DA neuron. [{sup 11}C]MP was prepared by O-{sup 11}C-alkylation of a protected derivative of ritalinic acid with labeled methyl iodide. Serial studies at baseline and after treatment with methylphenidate (0.5 mg/kg, 20 min prior); GBR 12909 (1.5 mg/kg; 30 min prior); tomoxetine (1.5 mg/kg, 20 min prior) and citalopram (2.0 mg/kg, 30 min prior) were performed to assess non-specific binding and binding to the DA, norepinephrine and serotonin transporters respectively. Only MP and GBR 12909 changed the SR/CB distribution volume ratio (decrease of 38 and 37% respectively) demonstrating selectivity for DA transporters over other monoamine transporters. We then pursued the synthesis of enantiomerically pure C-{sup 11} labeled d- and l-MP by using enantiomerically pure protected d- and l-ritalinic acids as precursors. A striking difference in SR/CB ratio (3.3 and 1.1 for d- and l-respectively at 1 hr. after i.v. injections) strongly suggests that the pharmacological specificity of MP resides entirely in the d-isomer and the binding of l-isomer was mostly non-specific. Further evaluations are underway. Radioligand reversibility, selectivity and the fact that MP is an approved drug are advantages of using [{sup 11}C]MP.

  18. Enantioselective nano liquid chromatographic separation of racemic pharmaceuticals: a facile one-pot in situ preparation of lipase-based polymer monoliths in capillary format.

    Science.gov (United States)

    Ahmed, Marwa; Ghanem, Ashraf

    2014-11-01

    New affinity monolithic capillary columns of 150 µm internal diameter were prepared in situ fused glass capillary via either immobilization or encapsulation of Candida antarctica lipase B (CALB) on or within polymer monoliths, respectively. The immobilized lipase-based monoliths were prepared via copolymerization of 19.1% monomers (8.9% MMA and 10.2% GMA), 19.8% EDMA, and 61.1% porogens (54.2% formamide and 6.9% 1-propanol) w/w or 20% GMA, 20% EDMA, and 60% porogens (51.6% cyclohexanol and 8.4% 1-dodecanol) in the presence of AIBN (1%) as a radical initiator. This was followed by pumping a solution of lipase through the capillaries and rinsing with potassium phosphate buffer. On the other hand, the encapsulated lipase-based monoliths were prepared via copolymerization of 20% monomers (GMA), 20% EDMA, and 60% porogens (48% 1-propanol, 6% 1,4-butanediol) or 16.4% monomers (16% BuMA, 0.4% SPMA), 23.6% EDMA, and 60% porogens (36% 1-propanol, 18% 1,4-butanediol along with 6% lipase aqueous solution in potassium phosphate buffer. The prepared capillary columns were investigated for the enantioselective nano liquid chromatographic separation of a set of different classes of racemic pharmaceuticals, namely, α- and β-blockers, antiinflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs, and antiarrhythmic drugs. Run-to-run repeatability was quite satisfactory. The encapsulated lipase-based capillary monolith showed better enantioselective separations of most of the investigated compounds. Baseline separation was achieved for alprenolol, atenolol, bromoglutithimide, carbuterol, chloropheneramine, cizolertine carbinol, 4-hydroxy-3-methoxymandelic acid, desmethylcizolertine, nomifensine, normetanephrine, and sulconazole under reversed phase chromatographic conditions. A speculation about the understanding of the chiral recognition mechanism of

  19. Formation of one-dimensional helical columns and excimerlike excited states by racemic quinoxaline-fused [7]carbohelicenes in the crystal.

    Science.gov (United States)

    Sakai, Hayato; Shinto, Sho; Araki, Yasuyuki; Wada, Takehiko; Sakanoue, Tomo; Takenobu, Taishi; Hasobe, Taku

    2014-08-01

    A series of quinoxaline-fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light-emitting properties and to control the packing structures in the crystal. The electrochemical and spectroscopic properties and excited-state dynamics of these compounds were investigated in detail. The first oxidation potentials of HeQu derivatives are approximately the same as that of unsubstituted reference [7]carbohelicene (Heli), whereas their first reduction potentials are shifted to the positive by about 0.7 V. The steady-state absorption, fluorescence, and circular dichroism spectra also became redshifted compared to those of Heli. The molecular orbitals and energy levels of the HOMO and LUMO states, calculated by DFT methods, support these trends. Moreover, the absolute fluorescence quantum yields of HeQu derivatives are about four times larger than that of Heli. The structural properties of the aggregated states were analyzed by single-crystal analysis. Introduction of appropriate substituents (i.e., 4-methoxyphenyl) in the HeQu unit enabled the construction of one-dimensional helical columns of racemic HeQu derivatives in the crystal state. Helix formation is based on intracolumn π-stacking between two neighboring [7]carbohelicenes and intercolumn CH⋅⋅⋅N interaction between a nitrogen atom of a quinoxaline unit and a hydrogen atom of a helicene unit. The time-resolved fluorescence spectra of single crystals clearly showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units.

  20. Research progress of racemic menthol by lipase kinetic resolution%脂肪酶转酯化和水解反应拆分薄荷醇的研究进展

    Institute of Scientific and Technical Information of China (English)

    念保义; 黄志华; 罗菊香; 牛玉

    2011-01-01

    In the investigation of resolution of racemic menthol, lipase is generally used because lipase has chemistry-, region-, and stereo-selectivity, and the operation with lipase is noted for reliable source, low-cost, and simple procedure. The research progress of racemic menthol resolution by lipase in the past 0 years is reviewed. Especially, potential industrial applications of the lipase catalytic approach and unit operations are covered by analyzing the processes of trans-esterification, hydrolysis reaction and influence factors. The optimal pathway of resolution is achieved by analyzing resolution routes of menthol and alternatives of acyl agent for trans-esterification of menthol. Future investigations of the resolution of racemic menthol by lipase are discussed.%在拆分薄荷醇的研究中,脂肪酶因具有化学、区域和立体选择性以及来源广泛,价廉、操作简单而得到普遍应用.本文从脂肪酶拆分薄荷醇的转酯化、水解反应的工艺和影响因素等方面,分析了脂肪酶动力学拆分过程的转酯化和水解反应的催化路径和特点,指出脂肪酶拆分薄荷醇的最佳路径和工艺选择.综述了近10年来脂肪酶拆分消旋体薄荷醇的研究进展,特别综述了具有工业化前景的脂肪酶催化拆分和单元操作工艺的研究进展.同时展望了未来脂肪酶拆分薄荷醇的研究方向.

  1. Synthesis of nano-sized stereoselective imprinted polymer by copolymerization of (S)-2-(acrylamido) propanoic acid and ethylene glycol dimethacrylate in the presence of racemic propranolol and copper ion

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, Taher, E-mail: talizadeh@ut.ac.ir [Department of Analytical Chemistry, Faculty of Chemistry, University College of Science, University of Tehran, P.O. Box 14155-6455, Tehran (Iran, Islamic Republic of); Bagherzadeh, Azam; Shamkhali, Amir Nasser [Department of Applied Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of)

    2016-06-01

    A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was obtained by reaction of (L)-alanine with acryloyl chloride. The resulting monomer was characterized by FT-IR and HNMR and then utilized for the preparation of chiral imprinted polymer (CIP). This was carried out by copolymerization of (L)-alanine-derived chiral monomer and ethylene glycol dimethacrylate, in the presence of racemic propranolol and copper nitrate, via precipitation polymerization technique, resulting in nano-sized networked polymer particles. The polymer obtained was characterized by scanning electron microscopy and FT-IR. The non-imprinted polymer was also synthesized and used as blank polymer. Density functional theory (DFT) was also employed to optimize the structures of two diasterometric ternary complexes, suspected to be created in the pre-polymerization step, by reaction of optically active isomers of propranolol, copper ion and (S)-2-(acrylamido) propanoic acid. Relative energies and other characteristics of the described complexes, calculated by the DFT, predicted the higher stability of (S)-propranolol involved complex, compared to (R)-propranolol participated complex. Practical batch extraction test which employed CIP as solid phase adsorbent, indicated that the CIP recognized selectively (S)-propranolol in the racemic mixture of propranolol; whereas, the non-imprinted polymer (NIP) showed no differentiation capability between two optically active isomers of propranolol. - Highlights: • A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was synthesized. • (S)-propranolol-selective imprinted polymer was synthesized using the chiral monomer. • Racemic propranolol mixed with Cu(II) was used as template in the imprinting. • Density functional theory was employed to clarify the imprinting mechanism. • (S)-propranolol-Cu(II) complex was shown to conduct the imprinting process.

  2. Dinuclear cadmium(II), zinc(II), and manganese(II), trinuclear nickel(II), and pentanuclear copper(II) complexes with novel macrocyclic and acyclic Schiff-base ligands having enantiopure or racemic camphoric diamine components.

    Science.gov (United States)

    Jiang, Jue-Chao; Chu, Zhao-Lian; Huang, Wei; Wang, Gang; You, Xiao-Zeng

    2010-07-05

    Four novel [3 + 3] Schiff-base macrocyclic ligands I-IV condensed from 2,6-diformyl-4-substituted phenols (R = CH(3) or Cl) and enantiopure or racemic camphoric diamines have been synthesized and characterized. Metal-ion complexations of these enantiopure and racemic [3 + 3] macrocyclic ligands with different cadmium(II), zinc(II), manganese(II), nickel(II), and copper(II) salts lead to the cleavage of Schiff-base C horizontal lineN double bonds and subsequent ring contraction of the macrocyclic ligands due to the size effects and the spatial restrictions of the coordination geometry of the central metals, the steric hindrance of ligands, and the counterions used. As a result, five [2 + 2] and one [1 + 2] dinuclear cadmium(II) complexes (1-6), two [2 + 2] dinuclear zinc(II) (7 and 8), and two [2 + 2] dinuclear manganese(II) (9 and 10) complexes together with one [1 + 1] trinuclear nickel(II) complex (11) and one [1 + 2] pentanuclear copper(II) complex (12), bearing enantiopure or racemic ligands, different substituent groups in the phenyl rings, and different anionic ligands (Cl(-), Br(-), OAc(-), and SCN(-)), have been obtained in which the chiral carbon atoms in the camphoric backbones are arranged in different ways (RRSS for the enantiopure ligands in 1, 2, 4, 5, and 7-10 and RSRS for the racemic ligands in 3, 6, 11, and 12). The steric hindrance effects of the methyl group bonded to one of the chiral carbon atoms of camphoric diamine units are believed to play important roles in the formation of the acyclic [1 + 1] trinuclear complex 11 and [1 + 2] dinuclear and pentanuclear complexes 6 and 12. In dinuclear cadmium(II), zinc(II), and manganese(II) complexes 1-10, the sequence of separations between the metal centers is consistent with that of the ionic radii shortened from cadmium(II) to manganese(II) to zinc(II) ions. Furthermore, UV-vis, circular dichroism, (1)H NMR, and fluorescence spectra have been used to characterize and compare the structural

  3. Syntheses, structures and photocatalytic properties of five new praseodymium-antimony oxochlorides: from discrete clusters to 3D inorganic-organic hybrid racemic compounds.

    Science.gov (United States)

    Zou, Guo-Dong; Wang, Ze-Ping; Song, Ying; Hu, Bing; Huang, Xiao-Ying

    2014-07-14

    Five novel praseodymium-antimony oxochloride (Pr-Sb-O-Cl) cluster-based compounds, namely (2-MepyH)2[Fe(1,10-phen)3]2[Pr4Sb12O18Cl14.6(OH)2.4(Hsal)]·H2O (1), (2-MepyH)2[Fe(1,10-phen)3]4{[Pr4Sb12O18Cl13.5(OH)0.5](bcpb)2[Pr4Sb12O18Cl13.5(OH)0.5]}·42H2O (2), (3-MepyH)2[Fe(1,10-phen)3]{[Pr4Sb12O18Cl13(H2O)2](bcpb)}·2(3-Mepy)·3H2O (3), [Fe(1,10-phen)3]2{[Pr4Sb12O18Cl10(H2O)2](bcpb)2}·3(3-Mepy)·13H2O (4), and (2-MepyH)6[Fe(1,10-phen)3]10{[Pr4Sb12O18Cl13(OH)2]2[Pr4Sb12O18Cl9][Pr4Sb12O18Cl9(OH)2]2(Hpdc)10(pdc)2}·110H2O (5) (2-Mepy = 2-methylpyridine, 3-Mepy = 3-methylpyridine, 1,10-phen = 1,10-phenanthroline, H2sal = salicylic acid, H3bcpb = 3,5-bis(4-carboxyphenoxy)benzoic acid, H3pdc = 3,5-pyrazoledicarboxylic acid) have been solvothermally synthesized and structurally characterized. Compound 1 is the first zero-dimensional (0D) Pr-Sb-O-Cl cluster decorated by an organic ligand. Compounds 2-4 are constructed from the same H3bcpb ligands but adopt different structures: 2 represents a rare example of a one-dimensional (1D) nanotubular structure based on high-nuclearity clusters; 3 exhibits a two-dimensional (2D) mono-layered structure, in which left-handed and right-handed helical chains are alternately arranged, while 4 features a double-layered structure with an unprecedented (3,3,6)-connected 3-nodal topological net. Compound 5 is a unique three-dimensional (3D) 2-fold interpenetrating racemic compound, simultaneously containing three kinds of Pr-Sb-O-Cl-pdc clusters. UV-light photocatalytic H2 evolution activity was observed for compound 3 with Pt as a co-catalyst and MeOH as a sacrificial electron donor. In addition, the magnetic properties of compounds 1 and 5 are also studied.

  4. Racemic carbohydrates - fact or fiction?

    DEFF Research Database (Denmark)

    Senning, Alexander Erich Eugen

    2007-01-01

    Chemical Abstracts Service has developed unsound practices in the naming and handling of simple carbohydrates such as aldopentoses 1, aldohexoses 2, and ketohexoses 3. Typically, the common name glucose is sometimes, inappropriately, interpreted as meaning DL-glucose DL-2d. Thus, a considerable...

  5. Nanoporous magnets of chiral and racemic [{Mn(HL)}2Mn{Mo(CN)7}2] with switchable ordering temperatures (TC = 85 K 106 K) driven by H2O sorption (L = N,N-dimethylalaninol).

    Science.gov (United States)

    Milon, Julie; Daniel, Marie-Christine; Kaiba, Abdellah; Guionneau, Philippe; Brandès, Stéphane; Sutter, Jean-Pascal

    2007-11-14

    Molecule-based solids represent a rare opportunity to combine, adjust, and interrelate structural and physical functionalities to develop multifunctional materials. Here we report on a series of porous supramolecular magnets whose magnetic properties are related to their sorption state. A family of magnets of the formula [{Mn(HL)(H2O)}2Mn{Mo(CN)7}2].2H2O have been obtained by assembling the heptacyano-metalate building unit {Mo(CN)7}4- with Mn(II) in the presence of protonated N,N-dimethylalaninol (L) as ligand, the latter being either as a racemic mixture or as a chiral R- or S-enantiomer. The resulting magnets possess an open framework structure and exhibit a TC with a switching behavior (TC = 85 K 106 K) as a function of the hydration state. Moreover, chiral magnets are formed with the optically active ligands. The H2O and gas (N2, CO2, CO) sorption features, the magnetic behavior of both the hydrated and dehydrated magnets, and the crystal structures of the hydrated chiral (S) and racemic magnets are described.

  6. Synthesis of nano-sized stereoselective imprinted polymer by copolymerization of (S)-2-(acrylamido) propanoic acid and ethylene glycol dimethacrylate in the presence of racemic propranolol and copper ion.

    Science.gov (United States)

    Alizadeh, Taher; Bagherzadeh, Azam; Shamkhali, Amir Nasser

    2016-06-01

    A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was obtained by reaction of (l)-alanine with acryloyl chloride. The resulting monomer was characterized by FT-IR and HNMR and then utilized for the preparation of chiral imprinted polymer (CIP). This was carried out by copolymerization of (l)-alanine-derived chiral monomer and ethylene glycol dimethacrylate, in the presence of racemic propranolol and copper nitrate, via precipitation polymerization technique, resulting in nano-sized networked polymer particles. The polymer obtained was characterized by scanning electron microscopy and FT-IR. The non-imprinted polymer was also synthesized and used as blank polymer. Density functional theory (DFT) was also employed to optimize the structures of two diasterometric ternary complexes, suspected to be created in the pre-polymerization step, by reaction of optically active isomers of propranolol, copper ion and (S)-2-(acrylamido) propanoic acid. Relative energies and other characteristics of the described complexes, calculated by the DFT, predicted the higher stability of (S)-propranolol involved complex, compared to (R)-propranolol participated complex. Practical batch extraction test which employed CIP as solid phase adsorbent, indicated that the CIP recognized selectively (S)-propranolol in the racemic mixture of propranolol; whereas, the non-imprinted polymer (NIP) showed no differentiation capability between two optically active isomers of propranolol. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Cholesteric Liquid-Crystal Copolyester, Poly[oxycarbonyl- 1,4-phenylene- oxy - 1,4 terephthaloyl- oxy- 1,4-phenylenecarbonyloxy (1,2-dodecane] [C34H36O8]n, Synthesized from Racemic Materials: Kinetics, Structure and Optical Characterization.

    Directory of Open Access Journals (Sweden)

    Mercedes Pérez Méndez

    2015-07-01

    Full Text Available The cholesteric liquid-crystal poly[oxycarbonyl-1,4-phenylene-oxy-1,4 terephthaloyl-oxy-1,4-phenylenecarbonyloxy(1,2-dodecane] [C34H36O8]n, named PTOBDME, synthesized by polycondensation reaction from equimolar quantities of TOBC and the racemic mixture of glycol (R-S-1,2 dodecanediol, exhibits unexpected optical activity and chiral morphology. The structure of racemic-PTOBDME, under different polymerization kinetics conditions, is analyzed by conventional NMR techniques and compared with those of polymer enantiomers R-PTOBDME and S-PTOBDME obtained starting R(+1,2 and S(-1,2-dodecanediol respectively. Molecular models based on the NMR signals intensities are proposed. The optical activity of racemicPTOBDME is evaluated by measuring the ORD values during kinetics study, and compared to the chiral polymers. Each enantiomeric polymer seems to present the same stereoregular head-tail, isotactic structure than the racemic, which we explain by the higher reactivity of the primary hydroxyl than the secondary one in the glycol through polycondensation. For each enantiomer, two independent sets of signals were observed by NMR, explained as two diastereomeric helical conformers: gg and gt, related with two possible staggered conformations, along the copolymer backbone. Chirality in racemic-PTOBDME is proposed to be due to the kinetic resolution of a preferable helical diastereomer, such as Sgt, with respect to the possible four forms, while the R/S ratio of asymmetric carbon atoms remained 50:50. Chiral amplification is observed in R-PTOBDME and S-PTOBDME due to a helical screw sense excess. Optimum yield was obtained for racemic PTOBDME, after 120 minutes polycondensated and decanted in toluene for 24 hours. Two weeks later a second fraction precipitated from the toluene mother liquor with 67.6% chiral excess. After eight months and two weeks a third fraction precipitated with 85.2% chiral excess.

  8. Phosphovanadylite: a new vanadium phosphate mineral with a zeolite-type structure

    Science.gov (United States)

    Medrano, M.D.; Evans, H.T.; Wenk, H.-R.; Piper, D.Z.

    1998-01-01

    Phosphovanadylite, whose simplified formula is (Ba,Ca,K,Na)x([(Va,Al)4P2(P,OH)16].12H2), is a new vanadium phosphate zeolite mineral found in the Phosphoria Formation at Monsanto's Enoch Valley Mine, Soda Springs, Idaho. Its formula in more detail is (Ba0.38Ca0.20K0.006Na0.02)??0.66 [P2(V3.44Al0.046)??3.90O10.34(OH)5.66] .12H2O. The drusy mineral occurs as pale greenish-blue euhedral cubes (20-50 ??m edge) coating phosphatic, organic-rich mudstone. The chemical composition determined by electron microprobe is (in weight percent) V-28.02, P-9.91, Al-1.97, Ca-1.31, Ba-8.28, Cd-0.09, Zn-0.34, Na-0.15, K-0.73, O-46.57, and F-0.03. The index of refraction is nD = 1.566 (4) and specific gravity is 2.16 (3). The X-ray powder pattern shows strong reflections at 3.16 A (422), 2.58 (600), 2.44 (620), and 7.73 (200), which are indexed on the basis of a cubic body-centered unit cell with a = 15.470 (4) A. From the single-crystal structure analysis, its space group was determined to be I43m, Z = 6, and its structure consists of V4O18 16 octahedral clusters linked to each other by P atoms to form a cubic lattice, creating cavities 7.0 and 5.5 A in diameter where mainly H2O resides. Final residual indexes are R = 0.066, Rw = 0.061, goodness-of-fit = 0.75, and 93 observations and 24 parameters.

  9. Ion beam analysis of zeolites type Li-ABW synthesized by hydrothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, E.; De Lucio, O. G.; Solis, C.; Zavala, E. P.; Cruz, J. [UNAM, Instituto de Fisica, Circuito Exterior, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Alfaro, S.; Rodriguez, C.; Valenzuela, M. A. [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Laboratorio de Catalisis y Materiales, Zacantenco, 07738 Mexico D. F. (Mexico); Rocha, M. F. [IPN, Escuela Superior de Ingenieria Mecanica y Electrica, Av. Instituto Politecnico Nacional s/n, Col. Lindavista, 07738 Mexico D. F. (Mexico); Murillo, G.; Policroniades, R. [ININ, Carretera Mexico-Toluca s/n, Ocoyoacac 52750, Estado de Mexico (Mexico)

    2010-02-15

    This work reports a method to synthesize and characterize Li-ABW zeolites by a hydrothermal method. These materials are good candidates for CO{sub 2} capture because of the high reactivity between the Li{sup +} with CO{sub 2} to form Li{sub 2}CO{sub 3}. We performed and elemental profile concentration using ion beam analysis. The elastic backscattered proton energy spectra from the Al, Si, O and Li nuclei, in combination with the {alpha} particles from the {sup 7}Li ({rho}, {alpha}){sup 4}He nuclear reaction energy spectra, were employed for this task. X-ray diffraction was also applied to determine the crystalline structure. (Author)

  10. Enantioselective excited-state quenching of racemic Tb (III) and Eu (III) Tris (pyridine-2,6-dicarboxylate) by vitamin B 12 derivatives

    Science.gov (United States)

    Meskers, Stefan C. J.; Dekkers, Harry P. J. M.

    1999-08-01

    Enantioselectivity in the dynamic quenching of the luminescence of the Δ and Λ enantiomers of racemic Tb(III)(pyridine-2,6-dicarboxylate=DPA) 33- and Eu(DPA) 33- by a series of corrinoids is demonstrated by time resolved luminescence and circular-polarization-of-luminescence (CPL) spectroscopy. Studied are cyanocobalamin (vitamin B 12), aquacobalamin (B 12a) and its conjugated base hydroxocobalamin (HOCbl), dicyanocobinamide ((CN) 2Cbi) and the heptamethyl ester of dicyanocobyrinic acid ((CN) 2Cby(OMe) 7). For this set of quenchers (Q), the diastereomeric quenching rate constants ( kqΔ and kqΛ) are reported together with the degree of enantioselectivity Eq=( kqΔ- kqΛ)/( kqΔ+ kqΛ). In the systems with Tb, values of the average rate constant kqavg(=( kqΔ+ kqΛ)/2) are 1.0, 2.9 and 0.53 10 8 M -1 s -1 for CNCbl, (CN) 2Cbi, (CN) 2Cby(OMe) 7 with Eq=-0.24, -0.20, +0.01 (standard error of Eq is 0.01). The quenching by B 12a is strongly dependent on pH and ionic strength ( I); when I=12 mM we find kqavg=5.3, Eq=-0.23 at pH 6.7 and kqavg=1.3, Eq=-0.27 at pH 8.9. Corresponding rates for Eu are 0.41, 27, 3.4 10 7 M -1 s -1 and for B 12a, 7.3 and 1.2 10 7 M -1 s -1, corresponding values for Eq -0.27, -0.29, +0.02, -0.21 and -0.29. The quenching reaction is modeled as a pre-equilibrium involving the formation of an encounter complex (association constant K) followed by the actual electronic energy transfer step (rate ket). By relating the quenching data with molecular structure it is argued that the binding in the encounter complex involves two hydrogen bonds between the uncoordinated carboxylate oxygen atom of two DPA ligands of Ln(DPA) 33- and two amide groups of the corrinoid, presumably involving the a and g, the a and b, or the b and g side chains. For some corrinoid/Ln(DPA) 33- complexes the association constants and enantioselectivities in the ground state are known (Spectrochimica Acta 55A (1999) 1837-1855), which allows for an estimate of the average rate of

  11. Bupivacaína racêmica, levobupivacaína e ropivacaína em anestesia loco-regional para oftalmologia: um estudo comparativo Racemic bupivacaine, levobupi vacaine and ropivacaine in regional anesthesia for ophtalmology: a comparative study

    Directory of Open Access Journals (Sweden)

    Edno Magalhães

    2004-04-01

    Full Text Available OBJETIVO: A bupivacaína racêmica, utilizada largamente em anestesia peribulbar devido à boa qualidade de bloqueio motor, apresenta menor margem de segurança para cardiotoxicidade em relação a ropivacaína e bupivacaína levógira. O objetivo deste estudo foi comparar o grau de bloqueio motor e alteração da pressão intra-ocular (PIO em anestesia peribulbar produzida pela bupivacaína racêmica, levobupivacaína e ropivacaína. MÉTODOS: Noventa e sete pacientes, estado físico I e II da classificação da Sociedade Americana de Anestesiologistas, submetidos a anestesia peribulbar, foram divididos em três grupos: grupo A-(n=16 bupivacaína racêmica 0,75% com adrenalina 1:200.000; grupo B -(n=16 bupivacaína levógira 0,75% com adrenalina 1:200.000; grupo C -(n=15 ropivacaína 0,75%. Utilizou-se 7ml da solução anestésica com 280 UI de hialuronidase, em punção única no rebordo orbital inferior. Foram registrados a PIO e grau de bloqueio motor 5 minutos antes da punção e 1, 2, 3, 4, 5 e 10 minutos após a punção. O bloqueio motor foi avaliado pela escala de Nicoll. Para a análise estatística, foram utilizados os testes de Wilcoxon, análise de freqüência simples e t de Student. Foi considerado significativo pBACKGROUND AND OBJECTIVE: Racemic bupivacaine, used in peribulbar anesthesia owing to its high potential to promote motor blockade, presents a smaller safety margin for cardiotoxicity in relation to ropivacaine and levobupivacaine. The objective of this study was to compare the degree of motor blockade and alteration of intraocular pressure (IOP produced by racemic bupivacaine, levobupivacaine and ropivacaine in peribulbar block. METHOD: Ninety seven patients, ASA physical status I and II, submitted to peribulbar anesthesia, were randomly allocated into three groups: group A-(n=16 receiving racemic bupivacaine 0.75% with epinephrine 1:200.000; group B -(n=16 levobupivacaine 0.75% with epinephrine 1:200.000; group C -(n=15

  12. Novel routes to either racemic or enantiopure α-amino-(4-hydroxy-pyrrolidin-3-yl)acetic acid derivatives and biological evaluation of a new promising pharmacological scaffold.

    Science.gov (United States)

    Cecioni, Samy; Aouadi, Kaïss; Guiard, Julie; Parrot, Sandrine; Strazielle, Nathalie; Blondel, Sandrine; Ghersi-Egea, Jean-François; Chapelle, Christian; Denoroy, Luc; Praly, Jean-Pierre

    2015-06-15

    Cycloaddition between (+) or (-)-menthone-derived nitrones and N-benzyl-3-pyrroline afforded enantiopure spiro-fused heterocycles. The reaction occurred enantio- and diastereo-selectively on the less hindered side of the nitrone, the 3-pyrroline N-benzyl group being oriented outwards, thus controlling the configurations of three simultaneously created chiral centers. From either (+) or (-)-menthone, both enantiomeric cycloadducts were synthesized in excellent yield. Removing the chiral auxiliary and the N-benzyl group delivered a series of enantiopure 4-hydroxy-3-glycinyl-pyrrolidine derivatives in 3-5 steps and 36 to 81 overall yields. Using two other achiral nitrones, shorter routes to racemic analogues were developed. Two of the synthesized compounds markedly lowered extracellular glutamate level and modestly interacted with cannabinoid type-1 receptors. As these two neuroactive compounds were devoid of in vitro toxicity and did not cross the blood brain interface, they might represent potential pharmacological agents to target peripheral organs.

  13. 有机介质中脂肪酶促动力学拆分外消旋1-三甲基硅乙醇%Lipase-catalyzed Kinetic Resolution of Racemic 1-Trimethylsilylethanol in Organic Solvent

    Institute of Scientific and Technical Information of China (English)

    吴虹; 宗敏华; 王菊芳; 罗涤衡; 娄文勇

    2004-01-01

    The enantioselective esterification of racemic 1-trimethylsilylethanol with acids catalyzed by lipase in organic solvent was successfully performed.The influence of some factors on the reaction was investigated.Among the four lipases explored,Candida rugosa lipase(CRL)showed the highest activity and enantioselectivity.Octanoic acid was the best acyl donor among the eleven acids studied and n-hexane was the most suitable medium for the reaction.The optimum shaking rate and temperature were found to be 150 r·min-1 and 20°C to 30°C,respectively.The enantiomeric excess of the remaining(S)-(-)-1-trimethylsilylethanol was 93% when substrate conversion was 53% upon incubation of the reaction mixture at 30°C,150 r·min-1 for 12 h.

  14. Influence of the raceme of order on the plants and processing systems in the quality of castor bean’s seed = Influência da ordem dos racemos na planta e sistemas de beneficiamento na qualidade de sementes de mamona

    Directory of Open Access Journals (Sweden)

    Katilayne Vieira de Almeida

    2012-04-01

    Full Text Available To obtain high quality seeds, required efficient and accurate control of all stages of production are required, from selecting seeds in the plant itself and processing. The objective of this study was to evaluate the influence of the order of racemes in fruit harvest and processing in three systems of quality of castor beans. The castor bean seeds were from the production field BRS 149 Nordestina, installed at the Experimental Station of Embrapa Algodão from Barbalha-CE. A completely randomized delineation was used, with a 3 x 3 factorial with four replications, where the factors were: harvest in three orders of racemes (primary, secondary, and tertiary harvested racemes and three systems of processing (manual, manual machine, and mechanical machine peeling. The seeds from each treatment were subjected to germination tests, vigor, purity analysis, water content, and oil content. The secondary and tertiary racemes produce seeds with high physiological quality in relation to primary. The seeds peeled by a mechanical peeler machine provided greater seedling length, while the seeds processed manually had higher oil content. = Para a obtenção de sementes de alta qualidade, é necessário o controle eficiente e rigoroso de todas as etapas de produção, desde a escolha das sementes na própria planta e beneficiamento. Objetivou-se com este trabalho avaliar a influência da ordem dos racemos na colheita dos frutos e de três sistemas de beneficiamento na qualidade das sementes de mamona. As sementes de mamoneira foram provenientes do campo de produção da cultivar BRS 149 Nordestina, instalado na Estação Experimental da Embrapa Algodão de Barbalha-CE. Foi adotado o delineamento inteiramente casualizado, usando-se o esquema fatorial de 3 x 3, com quatro repetições, onde os fatores foram: colheita em três ordens de racemos (frutos colhidos dos racemos primários, secundários e terciários e três sistemas de beneficiamento (manual, m

  15. A New Synthetic Route to Diastereomerically Pure Cyclopropane-Phosphorus Derivatives Utilizing the Chiron 5-L-Menthyloxy-3-bromo-2(5H)-furanone and Racemic Dialkyl α-Hydroxyalkanephosphonate

    Institute of Scientific and Technical Information of China (English)

    FAN,Xue-E(范雪娥); FU,Yu-Qin(傅玉琴); WANG,Jian-Ge(王建革); DU,Qiao-Yun(杜巧云); CHEN,Qing-Hua(陈庆华)

    2002-01-01

    A new chemical transformtion for the construction of diversely functionalized cyclopropane-phosphorus derivatives utilizing chiron 4 and racemic diethyl α-hydroxylbenzylphosphonate asthekey precursors is described. The diastereomeric pure phosphorus-containing derivatives 5a, 5′a, 5b and 5′b were obtained respectively, in good yields with d. e. ≥ 98% via asymmetric tandem double Michael addition/internal nucleeophilic substitution of the corresponding commpounds and further through the separation of the diastereomeric mixture by column chromatography. The diversely functionalized phosphorus derivatives are identified on the basis of their elemental analysis and spectroscopic data, such as IR, 1H NMR, 13C NMR and MS. The absolute configuration of the interesting cyclopropane-phosphorus compound 5a was established by X-ray crystallography. Thus,these results provide a valuable strategy for synthesizing some biologically active molecules.

  16. Produção e características físicas de sementes de mamoneira em função da posição do racemo e do fruto = Production and physical characteristics of castor bean seeds affected by raceme and fruit position

    Directory of Open Access Journals (Sweden)

    Carla Gomes Machado

    2009-04-01

    Full Text Available Para avaliar a produção e características físicas de sementes de mamoneira, em função da posição do racemo e do fruto, foi conduzido um trabalho, em condições de campo, em Nitossolo Vermelho Estruturado, no município de Botucatu, Estado de São Paulo. Utilizou-se a cultivar AL Guarany 2002, a qual teve seus três primeiros racemos colhidos e subdividos em três terços, os quais constituíram os tratamentos. Para avaliação das características físicas dos racemos e frutos, foi determinado o comprimento dosracemos, o número de frutos por racemo, a dimensão dos frutos, o peso dos frutos e o número de sementes por fruto. Para avaliação das características físicas das sementes, foi determinado o teor de água, o tamanho e a massa de 1.000, além de avaliação da produçãode sementes. Constatou-se que os tratamentos avaliados exerceram influência sobre as características físicas dos racemos, frutos e sementes e a produção de sementes de mamona; o número de frutos e a produção de sementes diretamente proporcionais foram menores deacordo com a formação dos racemos.With the objective of evaluating production and physical characteristics of castor bean seeds affected by raceme and fruit position, a study was carried out under field conditions, in a Red Nitosol (Afisol, in Botucatu, São Paulo State. The cultivar AL Guarany 2002 was used. Its three first racemes were harvested and divided into three parts, which consisted of the treatments. Raceme length, number of leaves per raceme, fruit dimensions, fruit weight and number of seeds per fruit were determined to evaluate physical characteristics of the racemes and fruits; seed moisture content, size and weight of thousand seeds and seed production were determined to evaluate physical characteristics of the seeds. The treatments influenced physical characteristics of the racemes, fruits and seeds, besides the production of castor bean seeds; the number of fruitsand the seed

  17. Dual Role of Hydrophobic Racemic Thioesters of α-Amino Acids in the Generation of Isotactic Peptides and Co-peptides in Water; Implications for the Origin of Homochirality

    Science.gov (United States)

    Illos, Roni A.; Clodic, Gilles; Bolbach, Gerard; Weissbuch, Isabelle; Lahav, Meir

    2010-02-01

    Thioesters of α-amino acids are considered as plausible monomers for the generation of the primeval peptides. DL-Leucine-thioethyl esters (LeuSEt), where the L-enantiomer was tagged with deuterium atoms, undergo polycondensation in water or in bicarbonate or imidazole buffer solutions to yield mainly heterochiral (atactic) peptides and diketopiperazine, as analyzed by MALDI-TOF and ESI mass-spectrometry. In variance, when polymerization of DL(d10) -Leu, first activated with N,N'-carbonyldiimidazole, then initiated with ethanethiol or with DL(d3) -LeuSEt yielded a library of peptides up to 30 detectable residues where those of homochiral sequence (isotactic) are the dominant diastereoisomers. At these conditions, racemic β-sheets are formed and operate as stereoselective templates in the process of chain-elongation. Isotopic L: L(d10)-Leu co-peptides were obtained in the polymerization of L(d10)-Leu with L-LeuSEt. By contrast, mixtures of oligo- D-Leu and oligo- L(d10)-Leu were obtained in the polymerization of mixtures of D-LeuSEt with activated L(d10)-Leu. Isotactic co-peptides containing Leu and Val residues were formed in the polymerization of mixtures of activated DL(d8)-Val with DL(d3) -LeuSEt in water, implying that the racemic β-sheets exert regio-enantio-selection but not chemo-selection. A reaction pathway is suggested, where LeuSEt operates both as initiator of the reaction as well as a multimer.

  18. (3R*,5′S*-6,7-Dimethoxy-3-(4′-methoxy-6′-methyl-5′,6′,7′,8′-tetrahydro-1,3-dioxolo[4,5-g]isoquinolin-5′-ylisobenzofuran-1(3H-one (racemic α-noscapine

    Directory of Open Access Journals (Sweden)

    Dieter Schinzer

    2010-03-01

    Full Text Available In the racemic title compound, C22H23NO7, the dihedral angle between the fused ring systems is 51.87 (6°. Two of the methoxy groups are disordered over two orientations in 0.688 (5:0.312 (5 and 0.672 (15:0.328 (15 ratios. In the crystal, weak C—H...O interactions link the molecules.

  19. Characterization of the Enantioselective Properties of the Quinohemoprotein Alcohol Dehydrogenase of Acetobacter pasteurianus LMG 1635. 1. Different Enantiomeric Ratios of Whole Cells and Purified Enzyme in the Kinetic Resolution of Racemic Glycidol.

    Science.gov (United States)

    Machado, S S; Wandel, U; Jongejan, J A; Straathof, A J; Duine, J A

    1999-01-01

    Resting cells of Acetobacter pasteurianus LMG 1635 (ATCC 12874) show appreciable enantioselectivity (E=16-18) in the oxidative kinetic resolution of racemic 2,3-epoxy-1-propanol, glycidol. Distinctly lower values (E=7-9) are observed for the ferricyanide-coupled oxidation of glycidol by the isolated quinohemoprotein alcohol dehydrogenase, QH-ADH, which is responsible for the enantiospecific oxidation step in whole cells. The accuracy of E-values from conversion experiments could be verified using complementary methods for the measurement of enantiomeric ratios. Effects of pH, detergent, the use of artificial electron acceptors, and the presence of intermediate aldehydes, could be accounted for. Measurements of E-values at successive stages of the purification showed that the drop in enantioselectivity correlates with the separation of QH-ADH from the cytoplasmic membrane. It is argued that the native arrangement of QH-ADH in the membrane-associated complex favors the higher E-values. The consequences of these findings for the use of whole cells versus purified enzymes in biocatalytic kinetic resolutions of chiral alcohols are discussed.

  20. 5,7-Dihydroxy-2-(4-hydroxyphenyl)chroman-4-one (naringenin): X-ray diffraction structures of the naringenin enantiomers and DFT evaluation of the preferred ground-state structures and thermodynamics for racemization

    Science.gov (United States)

    Nesterov, Volodymyr V.; Zakharov, Lev N.; Nesterov, Vladimir N.; Calderon, Jose G.; Longo, Antonella; Zaman, Khadiza; Choudhury, Feroza Kaneez; Farrell, William; Shulaev, Vladimir; Richmond, Michael G.

    2017-02-01

    The R- and S-enantiomers of naringenin were separated by chiral supercritical fluid (SCF) and the absolute configuration of each enantiomer was established by X-ray crystallography. The solid-state data is in agreement with the reported circular dichroism spectra. Both enantiomers crystallize in the monoclinic crystal system in the space group P21 with two independent molecules in the asymmetric unit. In all molecules, the pyrone ring adopts a flattened chair-like conformation in which the C1 atom deviates from the plane drawn through the remaining five atoms of this heterocycle. The 4-hydroxyphenyl substituent located at C1 of the pyrone ring occupies an equatorial position and lies in a plane that is almost perpendicular to the aromatic platform associated with the heterocyclic portion of the molecule. Strong intramolecular O-H⋯O hydrogen bonding exists between the carbonyl moiety and the aryl hydroxyl group at C5. In both enantiomers, a favorable mutual orientation of two independent molecules promotes the formation of intermolecular O-H⋯O hydrogen bonds that link them into dimers. There are additional long-range intermolecular O-H⋯O hydrogen bonds and weak C-H⋯O contacts within the unit cell of each enantiomer that connect dimers in an extended network. DFT calculations have been performed and the thermodynamics for naringenin racemization via an acyclic chalcone have been computed. Eight energetically accessible conformations have been verified for S-naringenin.

  1. Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4'-bipyridine cocrystal with their crystal structures.

    Science.gov (United States)

    Tamboli, Majid I; Bahadur, Vir; Gonnade, Rajesh G; Shashidhar, Mysore S

    2014-11-01

    Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8, (1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4'-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2, (1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In (1), molecules are assembled around the crystallographic twofold screw axis (b axis) to form a helical self-assembly through conventional O-H···O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El···Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O-H···N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

  2. Apparent shortening of the Csp(3)-Csp(3)bond analysed via a variable-temperature X-ray diffraction study in racemic 1,1'-binaphthalene-2,2'-diyl diethyl bis(carbonate).

    Science.gov (United States)

    Nayak, Susanta K; Chandrasekhar, S; Guru Row, T N

    2009-05-01

    Crystal structure determination at room temperature [292 (2) K] of racemic 1,1'-binaphthalene-2,2'-diyl diethyl bis(carbonate), C(26)H(22)O(6), showed that one of the terminal carbon-carbon bond lengths is very short [Csp(3)-Csp(3) = 1.327 (6) A]. The reason for such a short bond length has been analysed by collecting data sets on the same crystal at 393, 150 and 90 K. The values of the corrected bond lengths clearly suggest that the shortening is mainly due to positional disorder at two sites, with minor perturbations arising as a result of thermal vibrations. The positional disorder has been resolved in the analysis of the 90 K data following the changes in the unit-cell parameters for the data sets at 150 and 90 K, which appear to be an artifact of a near centre of symmetry relationship between the two independent molecules in the space group P1 at these temperatures. Indeed, the unit cell at low temperature (150 and 90 K) is a supercell of the room-temperature unit cell.

  3. Enzymes involved in the glycidaldehyde (2,3-epoxy-propanal) oxidation step in the kinetic resolution of racemic glycidol (2,3-epoxy-1-propanol) by Acetobacter pasteurianus.

    Science.gov (United States)

    Wandel, U; Machado, S S.; Jongejan, J A.; Duine, J A.

    2001-02-01

    It is already known that kinetic resolution of racemic glycidol (2,3-epoxy-1-propanol) takes place when Acetobacter pasteurianus oxidizes the compound to glycidic acid (2,3-epoxy-propionic acid) with glycidaldehyde (2,3-epoxy-propanal) proposed to be the transient seen in this conversion. Since inhibition affects the feasibility of a process based on this conversion in a negative sense, and the chemical reactivity of glycidaldehyde predicts that it could be the cause for the phenomena observed, it is important to know which enzyme(s) oxidise(s) this compound. To study this, rac.- as well as (R)-glycidaldehyde were prepared by chemical synthesis and analytical methods developed for their determination. It appears that purified quinohemoprotein alcohol dehydrogenase (QH-ADH type II), the enzyme responsible for the kinetic resolution of rac.-glycidol, also catalyses the oxidation of glycidaldehyde. In addition, a preparation exhibiting dye-linked aldehyde dehydrogenase activity for acetaldehyde, most probably originating from molybdohemoprotein aldehyde dehydrogenase (ALDH), which has been described for other Acetic acid bacteria, oxidised glycidaldehyde as well with a preference for the (R)-enantiomer, the selectivity quantified by an enantiomeric ratio (E) value of 7. From a comparison of the apparent kinetic parameter values of QH-ADH and ALDH, it is concluded that ALDH is mainly responsible for the removal of glycidaldehyde in conversions of glycidol catalysed by A. pasteurianus cells. It is shown that the transient observed in rac.-glycidol conversion by whole cells, is indeed (R)-glycidaldehyde. Since both QH-ADH and ALDH are responsible for vinegar production from ethanol by Acetobacters, growth and induction conditions optimal for this process seem also suited to yield cells with high catalytic performance with respect to kinetic resolution of glycidol and prevention of formation of inhibitory concentrations glycidaldehyde.

  4. Neuralgia do trigêmeo bilateral por cisticerco racemoso unilateral no ângulo-ponto cerebelar: relato de caso Unusual cause for bilateral trigeminal neuralgia: unilateral racemous cysticercus of cerebellopontine angle. Case report

    Directory of Open Access Journals (Sweden)

    PAULO HENRIQUE AGUIAR

    2000-12-01

    Full Text Available Descrevemos o caso de uma paciente de 42 anos portadora de cisticerco racemoso na região do ângulo ponto-cerebelar (APC direito com trigeminalgia bilateral mais intensa no lado ipsilateral à localização do parasita. O cisticerco foi totalmente removido por meio de craniotomia suboccipital. No primeiro dia pós-operatório houve desaparecimento bilateral da dor. Duas hipóteses fisiopatológicas foram aventadas para explicar a sintomatologia: lesões que ultrapassam os limites da cisterna do APC poderão através da cisterna pré-pontina alcançar a cisterna do APC atingindo o trigêmeo contralateral; lesões com grande efeito de massa poderão provocar rotação do tronco cerebral e deslocamento e tração de estruturas ipsi e contralaterais, provocando compressão arteriovenosa sobre o trigêmeo contralateral na porção superior da cisterna do APC. Salientamos a necessidade de exames de imagem ante qualquer algia craniofacial e observamos que, em lesões na região do APC, a cisticercose não pode ser esquecida.We report the case of a 42-year-old woman with a racemous cystecercus in the right cerebellopontine angle (CPA, who presented with bilateral trigeminal neuralgia. The parasite was completly removed via a right suboccipital craniotomy. On the first postoperative day, the patient indicated that the pain disappeared. The neuralgia was caused by two probable mechanisms: a distortion of the brain stem and compression of the nerve against an arterial loop at the entry zone or arachnoiditis caused by the parasite in the both CPA cisternae. This case demonstrates the advisability of obtaining imaging studies in all patients with trigeminal neuralgia before starting any management. We must always remind that the cysticercus may be a differential diagnosis of CPA lesions.

  5. Racemic alkaloids from the fungus Ganoderma cochlear.

    Science.gov (United States)

    Wang, Xin-Long; Dou, Man; Luo, Qi; Cheng, Li-Zhi; Yan, Yong-Ming; Li, Rong-Tao; Cheng, Yong-Xian

    2017-01-01

    Seven pairs of new alkaloid enantiomers, ganocochlearines C-I (1, 3-8), and three pairs of known alkaloids were isolated from the fruiting bodies of Ganoderma cochlear. The chemical structures of new compounds were elucidated on the basis of 1D and 2D NMR data. The absolute configurations of compounds 1, 3-10 were assigned by ECD calculations. Biological activities of these isolates against renal fibrosis were accessed in rat normal or diseased renal interstitial fibroblast cells. Importantly, the plausible biosynthetic pathway for this class of alkaloids was originally proposed.

  6. The γ-polymorph of AgZnPO4 with an ABW zeolite-type framework topology

    Directory of Open Access Journals (Sweden)

    Abderrazzak Assani

    2010-11-01

    Full Text Available The γ-polymorph of the title compound, silver zinc orthophosphate, was synthesized under hydrothermal conditions. The structure consists of ZnO4, PO4 and AgO4 units. The coordination spheres of ZnII and PV are tetrahedral, whereas the AgI atom is considerably distorted from a tetrahedral coordination. Each O atom is linked to each of the three cations. An elliptic eight-membered ring system is formed by corner-sharing of alternating PO4 and ZnO4 tetrahedra, leading to a framework with an ABW-type zeolite structure. The framework encloses channels running parallel to [100] in which the Ag cations are located, with Ag...Ag contacts of 3.099 (3 Å. This short distance results from d10...d10 interactions, which play a substantial role in the crystal packing. The structure of γ-AgZnPO4 is distinct from the two other polymorphs α-AgZnPO4 and β-AgZnPO4, but is isotypic with NaZnPO4-ABW, NaCoPO4-ABW and NH4CoPO4-ABW.

  7. The γ-polymorph of AgZnPO4 with an ABW zeolite-type framework topology

    Science.gov (United States)

    Assani, Abderrazzak; Saadi, Mohamed; El Ammari, Lahcen

    2010-01-01

    The γ-polymorph of the title compound, silver zinc orthophos­phate, was synthesized under hydro­thermal conditions. The structure consists of ZnO4, PO4 and AgO4 units. The coord­ination spheres of ZnII and PV are tetra­hedral, whereas the AgI atom is considerably distorted from a tetra­hedral coordination. Each O atom is linked to each of the three cations. An elliptic eight-membered ring system is formed by corner-sharing of alternating PO4 and ZnO4 tetra­hedra, leading to a framework with an ABW-type zeolite structure. The framework encloses channels running parallel to [100] in which the Ag cations are located, with Ag⋯Ag contacts of 3.099 (3) Å. This short distance results from d 10⋯d 10 inter­actions, which play a substantial role in the crystal packing. The structure of γ-AgZnPO4 is distinct from the two other polymorphs α-AgZnPO4 and β-AgZnPO4, but is isotypic with NaZnPO4-ABW, NaCoPO4-ABW and NH4CoPO4-ABW. PMID:21588789

  8. The γ-polymorph of AgZnPO4 with an ABW zeolite-type framework topology

    National Research Council Canada - National Science Library

    Abderrazzak Assani; Mohamed Saadi; Lahcen El Ammari

    2010-01-01

    .... Each O atom is linked to each of the three cations. An elliptic eight-membered ring system is formed by corner-sharing of alternating PO4 and ZnO4 tetrahedra, leading to a framework with an ABW-type zeolite structure...

  9. The γ-polymorph of AgZnPO4 with an ABW zeolite-type framework topology

    OpenAIRE

    Abderrazzak Assani; Mohamed Saadi; Lahcen El Ammari

    2010-01-01

    The γ-polymorph of the title compound, silver zinc orthophosphate, was synthesized under hydrothermal conditions. The structure consists of ZnO4, PO4 and AgO4 units. The coordination spheres of ZnII and PV are tetrahedral, whereas the AgI atom is considerably distorted from a tetrahedral coordination. Each O atom is linked to each of the three cations. An elliptic eight-membered ring system is formed by corner-sharing of alternating PO4 and ZnO4 tetrahedra, leading to a framework wit...

  10. The γ-polymorph of AgZnPO(4) with an ABW zeolite-type framework topology.

    Science.gov (United States)

    Assani, Abderrazzak; Saadi, Mohamed; El Ammari, Lahcen

    2010-10-02

    The γ-polymorph of the title compound, silver zinc orthophos-phate, was synthesized under hydro-thermal conditions. The structure consists of ZnO(4), PO(4) and AgO(4) units. The coord-ination spheres of Zn(II) and P(V) are tetra-hedral, whereas the Ag(I) atom is considerably distorted from a tetra-hedral coordination. Each O atom is linked to each of the three cations. An elliptic eight-membered ring system is formed by corner-sharing of alternating PO(4) and ZnO(4) tetra-hedra, leading to a framework with an ABW-type zeolite structure. The framework encloses channels running parallel to [100] in which the Ag cations are located, with Ag⋯Ag contacts of 3.099 (3) Å. This short distance results from d(10)⋯d(10) inter-actions, which play a substantial role in the crystal packing. The structure of γ-AgZnPO(4) is distinct from the two other polymorphs α-AgZnPO(4) and β-AgZnPO(4), but is isotypic with NaZnPO(4)-ABW, NaCoPO(4)-ABW and NH(4)CoPO(4)-ABW.

  11. The influence of lidocaine and racemic bupivacaine on neuromuscular blockade produced by rocuronium: a study in rat phrenic nerve-diaphragm preparation Influência da lidocaína e da bupivacaína racêmica no bloqueio neuromuscular produzido pelo rocurônio: estudo em preparação nervo frênico-diafragma de rato

    Directory of Open Access Journals (Sweden)

    Vanessa Henriques Carvalho

    2009-06-01

    Full Text Available PURPOSE: To evaluate in vitro lidocaine and racemic bupivacaine effects in neuromuscular transmission and in neuromuscular blockade produced by rocuronium. METHODS: Rats were distributed in 5 groups (n = 5 in agreement with the studied drugs: lidocaine, racemic bupivacaine, rocuronium, separately (Groups I, II, III; rocuronium in preparations exposed to local anesthetics (Groups IV, V. The concentrations used were: 20 µg/mL, 5 µg/mL and 4 µg/mL, for lidocaine, bupivacaine and rocuronium, respectively. It was evaluated: 1 amplitude of diaphragm muscle response to indirect stimulation, before and 60 minutes after separately addition of lidocaine, racemic bupivacaine and rocuronium and the association of local anesthetics - rocuronium; 2 membrane potentials (MP and miniature end-plate potentials (MEPP. RESULTS: Lidocaine and bupivacaine separately didn't alter the amplitude of muscle response and MP. In preparations previously exposed to lidocaine and racemic bupivacaine, the rocuronium blockade was significantly larger (90.10 ± 9.15% and 100%, respectively, in relation to the produced by rocuronium separately (73.12 ± 9.89%. Lidocaine caused an increase in the frequency of MEPP, being followed by blockade; racemic bupivacaine produced decrease being followed by blockade. CONCLUSIONS: Local anesthetics potentiated the blockade caused by rocuronium. The alterations of MEPP identify presynaptic action.OBJETIVO: Avaliar in vitro os efeitos da lidocaína e bupivacaína racêmica na transmissão neuromuscular e no bloqueio neuromuscular produzido pelo rocurônio. MÉTODOS: Ratos foram distribuídos em 5 grupos (n = 5 de acordo com a droga estudada: lidocaina, bupivacaína racêmica, rocurônio, isoladamente (Grupos I, II, III; rocurõnio em preparações expostas aos anestésicos locais (Grupos IV, V. As concentrações utilizadas foram: 20 µg/mL, 5 µg/mL e 4 µg/mL, para lidocaína, bupivacaína e rocurônio, respectivamente. Avaliou-se: 1

  12. Improved synthesis and pharmacological evaluation of racemic 11-demethylcalanolide A%消旋11-去甲胡桐素A的合成方法改进及其药理学评价

    Institute of Scientific and Technical Information of China (English)

    王琳; 彭宗根; 周春梅; 高琦; 刘刚; 张兴权; 陈鸿珊; 陶佩珍; 李燕; 白玉; 扈金萍; 马涛; 邢振堂

    2008-01-01

    An improved and practical synthesis of racemic 11-demethylcalanolide A [(±)-1] was developed. This improved process involved Pechmann reaction on phloroglucinol with ethyl butyrylacetate to give 5, 7,-dihydroxy-4-n-propylcoumarin(3). Poly phosphoric acid (PPA) catalyzed acylation of compound(3) with crotonic acid, then intramolecular cyclization was achieved simultaneously in one step to afford the key intermediate chromanone(4). A microwave assisted synthetic method preparing chromene(6) using chromenynation of chromanone(4) with 1, 1-diethoxy-methyl-2-butene was conducted. Luche reduction of chromene(6) using NaBH with CeCl3·7H2O preferably gave (±)-1. The overall yield of this four step synthesis of (±)-1 was around 32% increasing one fold more than that of the previous method. An in vitro investigation showed that (±)-1 exhibited inhibitory activities against both wild-type and drug-resistant HIV-1 in HIV-1 RT and cell culture assay, and significant synergistic effects in combination with AZT, T-20, and indinavir. Its LD50 of acute toxicity in mice by intragastric administration and by intraperitoneal injection were 735.65mg·kg-1 and 525.10mg·kg-1, respectively. The C and AUC were 0.54μg·mL-1 and 1.08(μg·mL-1)·h, respectively. The dynamics study of the inhibition of mice sera on HIV-1 RT showed that mice treated with 100mg·kg-1 (±)-1 once intraperitoneally were similar to that of 5mg·kg-1 of known clinical effective anti-HIV-1 drug neverapine. The results suggested that further investigation of the anti-HIV candidate (±)-1 was warranted.%本文发展一个实用改进方法以合成具有抗人免疫缺陷病毒(HIV-1)的天然产物的类似物11-去甲胡桐素A[(±)-1],方法改进包括以间苯三酚为起始原料与正丁酰乙酸乙酯在饱和氯化氢甲醇存在下,经过Pechmann反应生成5,7-双羟基-4-正丙基香豆素(3),再与巴豆酸用多聚磷酸作溶剂及催化剂进行酰化,同时分子内环合得到收率为70%关

  13. 磷酸锌氨的固相合成与表征%Solid- State synthesis and characterization of ammonium zincophosphate

    Institute of Scientific and Technical Information of China (English)

    王金霞; 高艳阳

    2005-01-01

    采用固相合成方法,以Zn(Ac)2·2H2O和(NH4)2HPO4为反应原料,于80℃反应4h合成磷酸锌氨化合物.使用化学分析、热重分析和XRD等方法对产物进行了表征.结果表明,采用固相方法能在低温短时内合成磷酸锌类化合物.

  14. Design and characterization of chitosan/zeolite composite films--Effect of zeolite type and zeolite dose on the film properties.

    Science.gov (United States)

    Barbosa, Gustavo P; Debone, Henrique S; Severino, Patrícia; Souto, Eliana B; da Silva, Classius F

    2016-03-01

    Chitosan films can be used as wound dressings for the treatment of chronic wounds and severe burns. The antimicrobial properties of these films may be enhanced by the addition of silver. Despite the antimicrobial activity of silver, several studies have reported the cytotoxicity as a factor limiting its biomedical applications. This problem may, however, be circumvented by the provision of sustained release of silver. Silver zeolites can be used as drug delivery platforms to extend the release of silver. The objective of this study was to evaluate the addition of clinoptilolite and A-type zeolites in chitosan films. Sodium zeolites were initially subjected to ion-exchange in a batch reactor. Films were prepared by casting technique using a 2% w/w chitosan solution and two zeolite doses (0.1 or 0.2% w/w). Films were characterized by thermal analysis, color analysis, scanning electron microscopy, X-ray diffraction, and water vapor permeation. The results showed that films present potential for application as dressing. The water vapor permeability is one of the main properties in wound dressings, the best results were obtained for A-type zeolite/chitosan films, which presented a brief reduction of this property in relation to zeolite-free chitosan film. On the other hand, the films containing clinoptilolite showed lower water vapor permeation, which may be also explained by the best distribution of the particles into the polymer which also promoted greater thermal resistance.

  15. Design and characterization of chitosan/zeolite composite films — Effect of zeolite type and zeolite dose on the film properties

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, Gustavo P.; Debone, Henrique S. [Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Diadema (Brazil); Severino, Patrícia [Universidade Tiradentes, Instituto de Tecnologia e Pesquisa, Aracaju (Brazil); Souto, Eliana B. [Department of Pharmaceutical Technology, Faculty of Pharmacy, University of Coimbra (FFUC), Pólo das Ciências da Saúde, Azinhaga de Santa Comba, 3000-548, Coimbra (Portugal); Center for Neuroscience and Cell Biology & Institute for Biomedical Imaging and Life Sciences (CNC-IBILI), University of Coimbra, Pólo das Ciências da Saúde, Azinhaga de Santa Comba, 3000-548, Coimbra (Portugal); Silva, Classius F. da, E-mail: cfsilva@unifesp.br [Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Diadema (Brazil)

    2016-03-01

    Chitosan films can be used as wound dressings for the treatment of chronic wounds and severe burns. The antimicrobial properties of these films may be enhanced by the addition of silver. Despite the antimicrobial activity of silver, several studies have reported the cytotoxicity as a factor limiting its biomedical applications. This problem may, however, be circumvented by the provision of sustained release of silver. Silver zeolites can be used as drug delivery platforms to extend the release of silver. The objective of this study was to evaluate the addition of clinoptilolite and A-type zeolites in chitosan films. Sodium zeolites were initially subjected to ion-exchange in a batch reactor. Films were prepared by casting technique using a 2% w/w chitosan solution and two zeolite doses (0.1 or 0.2% w/w). Films were characterized by thermal analysis, color analysis, scanning electron microscopy, X-ray diffraction, and water vapor permeation. The results showed that films present potential for application as dressing. The water vapor permeability is one of the main properties in wound dressings, the best results were obtained for A-type zeolite/chitosan films, which presented a brief reduction of this property in relation to zeolite-free chitosan film. On the other hand, the films containing clinoptilolite showed lower water vapor permeation, which may be also explained by the best distribution of the particles into the polymer which also promoted greater thermal resistance. - Highlights: • Zeolite/chitosan composite films were prepared by casting technique. • Micrographs showed slight difference according to the content and A-type zeolite. • The barrier properties of the films were suitable to the dressing application. • Film characterization suggested that zeolites interacted with the chitosan chain.

  16. Selective gas adsorption and unique structural topology of a highly stable guest-free zeolite-type MOF material with N-rich chiral open channels.

    Science.gov (United States)

    Li, Jian-Rong; Tao, Ying; Yu, Qun; Bu, Xian-He; Sakamoto, Hirotoshi; Kitagawa, Susumu

    2008-01-01

    A new multifunctional di-topic tetrazolate-based ligand, 2,3-di-1H-tetrazol-5-ylpyrazine (H(2)dtp) has been designed and synthesized. The solvothermal reaction of this ligand with ZnCl(2) gave a robust guest-free three-dimensional zeolite-like chiral metal-organic framework (MOF) complex, [Zn(dtp)], which crystallized in chiral space group P6(1) and possessed chiral open channels with nitrogen-rich walls and the diameter of approximately 4.1 A. This framework presents a unique uniform etd (8,3) topology, is the first example of its type in MOFs, and exhibits high thermal stability with the decomposition temperature above 380 degrees C and permanent porosity. It is interesting that this material is able to selectively adsorb O(2) and CO(2) over N(2) gas, being a rare example in MOFs. In addition, C(2)H(2) and MeOH adsorption results show that although the framework channel holds nitrogen-rich walls that may provide H-bonding sites, no NH H-bond effect between the guest molecules and microporous surface was observed.

  17. Structural characterization and Hirshfeld surface analysis of racemic baclofen

    Science.gov (United States)

    Maniukiewicz, Waldemar; Oracz, Monika; Sieroń, Lesław

    2016-11-01

    The crystal structure of baclofen, (R,S) [4-amino-3-(4-chlorophenyl)butanoic acid], (C10H12ClNO2, Mr = 213.66) has been determined by single crystal X-ray diffraction analysis. The title compound crystallizes in the orthorhombic space group Pbca (No. 61) with a = 9.2704(5), b = 7.0397(4), c = 30.4015(15) Å, V = 1984.0(2) Å3 and Z = 8. The molecules exist as zwitterions, adopting a gauche conformation with respect to the Cαsbnd Cβ bond, and held in a cross-linked chain arrangement by strong Nsbnd H⋯O hydrogen bonds and Csbnd Cl⋯π interactions. The electrostatic molecular potential as well as the intermolecular interactions of the title compound were analyzed by the Hirshfeld surfaces. The FT-IR spectrum is also reported. The DTA, TG and DTG results indicate that baclofen is stable up to 205 °C.

  18. Lipase catalyse glycerolysis for kinetic resolution of racemates.

    Science.gov (United States)

    Dlugy, C; Wolfson, A

    2007-09-01

    Candida antarctica lipase B catalyzed kinetic resolution of representative secondary alcohols, esters, and amine was successfully performed using triacetin or glycerol as solvents and acyl donor/acceptor. High conversions and enantioselectivities were achieved and the product was easily separated by simple extraction with diethyl ether.

  19. Enantioseparation of racemic aminoglutethimide using asynchronous simulated moving bed chromatography.

    Science.gov (United States)

    Lin, Xiaojian; Gong, Rujin; Li, Jiaxu; Li, Ping; Yu, Jianguo; Rodrigues, Alirio E

    2016-10-07

    The separation of aminoglutethimide enantiomers by the continuous multicolumn chromatographic processes were investigated experimentally and theoretically, where the columns were packed with cellulose tris 3,5-dimethylphenyl-carbamate stationary phase (brand name Chiralcel OD) and mobile phase was a mixture of n-hexane and ethanol with monoethanolamine additive. The continuous enantioseparation processes included a synchronous shifting process (SMB) and an asynchronous shifting process (VARICOL), which allowed reducing the column number (here from six-column SMB to five-column VARICOL process). Transport-dispersive model with the consideration of both intraparticle mass transfer resistance and axial dispersion was adopted to design and optimize the operation conditions for the separation of aminoglutethimide enantiomers by SMB process and VARICOL process. According to the optimized operation conditions, experiments were carried out on VARICOL-Micro unit using five-column VARICOL process with 1/1.5/1.5/1 configuration and six-column SMB process with 1/2/2/1 configuration. Products of R-aminoglutethimide (R-AG) enantiomer and S-aminoglutethimide (S-AG) enantiomer with more than 99.0% purity were obtained continuously from extract stream and raffinate stream, respectively. Furthermore, the experiemntal data obtained from five-column VARICOL process were compared with that from six-column SMB process, the feasibility and efficiency for the separation of guaifenesin enantiomers by VARICOL processes were evaluated. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Racemic calcium tartrate tetrahydrate [form (II)] in rat urinary stones.

    Science.gov (United States)

    Le Bail, A; Bazin, D; Daudon, M; Brochot, A; Robbez-Masson, V; Maisonneuve, V

    2009-06-01

    The title compound, [Ca(C4H4O6)].4H2O, calcium tartrate tetrahydrate, is a new triclinic centrosymmetric form identified in rat kidney calculus. The crystal structure was determined from powder and single-crystal X-ray diffraction. The four water molecules belong to one square face of the Ca-atom coordination (a square antiprism), the four O atoms of the second square face coming from two tartrate anions, building infinite chains alternating Ca atom polyhedra and tartrate anions along a, with the chains cross-linked by a network of hydrogen bonds.

  1. Genetics of Gossypol Content and Its Racemic Forms

    Institute of Scientific and Technical Information of China (English)

    SCHEFFLER Jodi; ROMANO Gabriela

    2008-01-01

    @@ Our goal is to develop elite lines with low total gossypol levels in the seed using conventional genetic techniques.There are a number of ways to reduce seed gossypol,including mechanical processes to remove gossypol from cottonseed products.However,these treatments add cost to the products and reduce the nutritional value of the resulting cottonseed meal.

  2. 手性磷酸锌钠的低热固相合成及调控%Synthesis and regulation of chiral sodium zincophosphate via low heat solid state reaction

    Institute of Scientific and Technical Information of China (English)

    周龙昌; 吴洪特; 廖森; 吴文伟; 孙雅博; 田晓珍

    2008-01-01

    对合成多孔功能材料手性磷酸锌钠的新方法进行了研究,以聚乙二醇-400 (PEG-400)为表面活性剂,Na3PO4·12H2O和无机锌盐为原料,用低热固相反应一步法成功合成得到P6122空间群的手性NaZnPO4·H2O.实验考察了不同的锌盐、磷酸盐,以及不同pH值对产物的影响.结果表明, pH值起着重要的作用,其调控着产物的结构;锌盐的种类不影响产物的结构;磷酸盐的种类则通过pH值的调控作用对产物产生影响.当pH在11、7~9、5、3左右时,得到的产物分别为(1) P6122空间群的手性NaZnPO4·H2O与非手性的NaZnPO4(OH)的混合物;(2)P6122空间群的手性的 NaZnPO4·H2O;(3)非手性的NaH(ZnPO4)2;(4)非手性的Zn3(PO4)2·4H2O.以PEG-400为表面活性剂,Na3PO4·12H2O及无机锌盐为原料,在P/Zn=1.18(摩尔比),pH=7~9,反应混合物于50℃陈化6 h的条件下,合成产物为手性NaZnPO4·H2O.

  3. Avaliação da cetamina racêmica e do isômero S(+, associados ou não a baixas doses de fentanil, na balneoterapia do grande queimado Evaluación de la cetamina racémica y del isómero S(+, asociados o no a bajas dosis de fentanil, en la balneoterapia del gran quemado Assessment of the use of racemic ketamine and its S(+ isomer, associated or not with low doses of fentanyl, in balneotherapy for major burn patients

    Directory of Open Access Journals (Sweden)

    Fernando Antônio de Freitas Cantinho

    2009-08-01

    severe painful stimuli. The objective of this study was to assess the safety and efficacy of different drug combinations in anesthesia for balneotherapy. METHODS: After approval by the Ethics Commission, 200 procedures of balneotherapy in 87 major burn adult patients were evaluated. Midazolam was used in all cases. The vials of ketamine were numbered and, therefore, at the time of the use, one did not know whether racemic or S(+ketamine was being used. Each morning it was decided by drawing lots whether fentanyl would be used or not in the procedures of that day. Patients were included in one of four groups: ISO/sf (S(+ isomer without fentanyl, ISO/cf (S(+ isomer with fentanyl, RAC/sf (racemic ketamine without fentanyl, and RAC/cf (racemic ketamine with fentanyl. The initial doses proposed were as follows: midazolam, 0.06 mg.kg-1; ketamine, 1.0 to 1.1 mg.kg-1; and fentanyl, 0.8 ¼g.kg1-1; additional doses were administered as needed. RESULTS: Only one patient recalled the pain of balneotherapy. In the group that received S(+ketamine, the use of fentanyl did not bring additional advantages; however, when associated with racemic ketamine, fentanyl reduced the total dose and the number of ketamine boluses. The extension of body surface burned was the main determinant of the severity of post-procedure pain. Reduced pain severity was the main factor considered by patients when grading their satisfaction with the anesthesia. CONCLUSIONS: The four different drug combinations proved to be safe and guaranteed the absence of pain during balneotherapy. Characteristics not directly related to the anesthetics proved to be more important in the incidence of post-procedure pain, which was the main factor considered by major burn patient to define their satisfaction with the anesthesia used.

  4. First synthesis of racemic saphenamycin and its enantiomers. Investigation of biological activity

    DEFF Research Database (Denmark)

    Laursen, Jane B.; Jorgensen, C.G.; Nielsen, John

    2003-01-01

    was observed in activity of the enantiomers of saphenamycin, which revealed that the chirality of saphenamycin has no consequences for the antibiotic activity. Saphenamycin proved to be a potent antibiotic against fusidic acid and rifampicin resistant S. aureus strains showing MIC of 0.1-0.2 mug/mL....

  5. Behavioral effects in monkeys of racemates of two biologically active marijuana constituents.

    Science.gov (United States)

    Scheckel, C L; Boff, E; Dahlen, P; Smart, T

    1968-06-28

    Both dl-Delta(8)- and dl-Delta(9)-tetrahydrocannabinol produced marked alterations of behavior in rhesus and squirrel monkeys. Squirrel monkeys appeared to have visual hallucinations. Continuous avoidance behavior of squirrel monkeys was stimulated by both drugs, but high doses of dl-Delta(9)-tetrahydrocannabinol also caused depression after the stimulant phase. Complex behavior involving memory and visual discrimination in rhesus monkeys was markedly disrupted by both drugs.

  6. Stereoselective amination of racemic sec-alcohols through sequential application of laccases and transaminases

    OpenAIRE

    Martínez, Lía; Gotor,Vicente; Lavandera, Ivan

    2016-01-01

    A one-pot/two-step bienzymatic asymmetric amination of secondary alcohols is disclosed. The approach is based on a sequential strategy involving the use of a laccase/TEMPO catalytic system for the oxidation of alcohols into ketone intermediates, and their following transformation into optically enriched amines by using transaminases. Individual optimizations of the oxidation and biotransamination reactions have been carried out, studying later their applicability in a concurrent proc...

  7. Separation of racemic mixture by ultrafiltration of enantioselective micelles. 2 (De) complexation kinetics

    NARCIS (Netherlands)

    Overdevest, P.E.M.; Schutyser, M.A.I.; Bruin, de T.J.M.; Riet, van 't K.; Keurentjes, J.T.F.; Padt, van der A.

    2001-01-01

    The application of enantioselective micelles in ultrafiltration systems can be an alternative route to meet the increasing demand for enantiopure products. We have studied the separation of D,L-phenylalanine (Phe) by cholesteryl-L-glutamate:CuII (CLG:CuII) anchored in nonionic micelles (intrinsic en

  8. Racemic tricarbonyl[7-methoxy-2-(η6-phenylchromane]chromium(0

    Directory of Open Access Journals (Sweden)

    Mukut Gohain

    2011-04-01

    Full Text Available In the title compound, [Cr(C16H16O2(CO3], the Cr0 atom of the Cr(CO3 unit is coordinated to the phenyl ring of the flavan ligand in an η6 mode, with a normal arene-to-metal distance. The Cr(CO3 unit exhibits a three-legged piano-stool conformation, while the dihydropyran ring displays a distorted envelope configuration. The phenyl ring is twisted away from the fused ring system by 25.5 (2°. The methoxy group is almost coplanar with the phenyl ring [CMe—O—Car—Car torsion angle = 8.46 (2°]. The crystal packing is stabilized by intermolecular C—H...O interactions.

  9. Thermodynamic studies of induced antiferroelectric phases in chiral and racemic systems

    Science.gov (United States)

    Filipowicz, M.; Kula, P.; Czuprynski, Krzysztof

    2004-09-01

    Bi- and multicomponent mixtures consisted of two groups of synclinic chiral esters: first one with a partially fluorinated terminal chain and the second one with hydrogenated terminal chain have been used for investigations. For some systems the induction of the anticlinic smectic CA* phase was observed. Enthalpies of the phase transitions for the systems with induced smectic CA phase upon compositions and specific heat were measured by DSC method.

  10. Hollow fiber liquid-supported membrane technology for enantioseparation of racemic salbutamol by combinatorial chiral selectors

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Enantioseparation of salbutamol solute was carried out in liquid-supported membrane by using a polyvinylidene fluoride hollow-fiber module. The enantioselective transport of solute was facilitated by combinatorial chiral selectors, which were dissolved in toluene organic solvent. The effects of molar concentration ratios of salbutamol to combinatorial chiral selectors, and the pH value of buffer solution on enantioseparation were investigated. The results show that when the molar concentration ratio is 2: 1:1, the maximum separation factor and enantiomer excess are 1.49 and 19.74%, respectively, and the R-enantiomer flux is more than S-enantiomer; the pH value of buffer solution influences the performances of enantioseparartion obviously, and the appropriate range of pH value is7.0-7.2.

  11. Asymmetric Suzuki-Miyaura coupling of heterocycles via Rhodium-catalysed allylic arylation of racemates

    Science.gov (United States)

    Schäfer, Philipp; Palacin, Thomas; Sidera, Mireia; Fletcher, Stephen P.

    2017-06-01

    Using asymmetric catalysis to simultaneously form carbon-carbon bonds and generate single isomer products is strategically important. Suzuki-Miyaura cross-coupling is widely used in the academic and industrial sectors to synthesize drugs, agrochemicals and biologically active and advanced materials. However, widely applicable enantioselective Suzuki-Miyaura variations to provide 3D molecules remain elusive. Here we report a rhodium-catalysed asymmetric Suzuki-Miyaura reaction with important partners including aryls, vinyls, heteroaromatics and heterocycles. The method can be used to couple two heterocyclic species so the highly enantioenriched products have a wide array of cores. We show that pyridine boronic acids are unsuitable, but they can be halogen-modified at the 2-position to undergo reaction, and this halogen can then be removed or used to facilitate further reactions. The method is used to synthesize isoanabasine, preclamol, and niraparib--an anticancer agent in several clinical trials. We anticipate this method will be a useful tool in drug synthesis and discovery.

  12. An Integrated Experimental and Computational Approach for Characterizing the Kinetics and Mechanism of Triadimefon Racemization

    Science.gov (United States)

    Enantiomers of chiral molecules commonly exhibit different environmental fates, pharmacokinetics, and toxicities. Ignoring these differences can introduce significant uncertainty when modeling the physiological and environmental fate of chlral chemicals and evaluating their risk ...

  13. Volume anestésico mínimo para bloqueio retrobulbar extraconal: comparação entre soluções a 0,5% de bupivacaína racêmica, de levobupivacaína e da mistura enantiomérica S75/R25 de bupivacaína Volumen anestésico mínimo para bloqueo retrobulbar extraconal: comparación entre soluciones a 0,5% de bupivacaína racémica, de levobupivacaína y de la mezcla enantiomérica S75/R25 de bupivacaína Minimum anesthetic volumes for extraconal retrobulbar block: comparison between 0.5% racemic bupivacaine, levobupivacaine and enantiomeric mixture S75/R25 bupivacaine

    Directory of Open Access Journals (Sweden)

    Luiz Fernando Soares

    2005-06-01

    después de 10 minutos como: 0 (ausente, 1 (diminuida ó 2 (normal. La suma de los resultados constituyó el resultado total de movilidad (ETM del globo ocular. El volumen inicial fue de 7,4 mL. Los volúmenes utilizados en pacientes subsiguientes correspondieron 0,1 unidad logarítmica mayor (ETM > 2 ó menor (ETM BACKGROUND AND OBJECTIVES: Minimum anesthetic volume (MAV of local anesthetics corresponds to the effective volume for regional anesthesia in 50% of patients. In this study, MAV of 0.5% racemic bupivacaine, 0.5% levobupivacaine and enantiomeric S75/R25 bupivacaine were calculated and compared. METHODS: This study involved two series of patients undergoing cataract extraction. Series 1 patients received either 0.5% racemic bupivacaine (n = 9 or 0.5% levobupivacaine (n = 11. Series 2 patients received either 0.5% racemic bupivacaine (n = 11 or 0.5% enantiomeric S75/R25 bupivacaine (n = 10. Blockades were achieved by single-injection and inferior-lateral approach. Motility of each rectus muscle was assessed 10 minutes later as: 0 (absent, 1 (decreased or 2 (normal. Total muscle scores represented total eye motility score (TMS. Local anesthetic volume administered to the first patient of each group was 7.4 mL. Subsequent patients received volumes corresponding to 0.1 higher natural logarithm unit (if TME > 2 or lower (if TME < 2 as compared to natural logarithm of preceding volume. Massey and Dixon's formulae were used for MAV calculations. RESULTS: MAVs of bupivacaine in both series were 6 mL and 6.2 mL, respectively. MAVs of levobupivacaine and enantiomeric S75/R25 bupivacaine were 5.7 mL and 5.8 mL, respectively. There were no differences between groups in effective anesthetic volumes. CONCLUSIONS: Similar volumes of 0.5% racemic bupivacaine, 0.5% levobupivacaine and enantiomeric S75/R25 bupivacaine are needed for extraconal retrobulbar anesthesia.

  14. Anestesia peridural para cesariana: estudo comparativo entre Bupivacaína Racêmica (S50-R50 e Bupivacaína com excesso enantiomérico de 50% (S75-R25 a 0,5% associadas ao Sufentanil Anestesia epidural para cesárea: estudio comparativo entre Bupivacaína Racémica (S50-R50 y Bupivacaína con exceso enantiomérico de 50% (S75-R25 a 0,5% asociadas al Sufentanil Epidural block for cesarean section: a comparative study between 0.5% racemic Bupivacaine (S50-R50 and 0.5% enantiomeric excess Bupivacaine (S75-R25 associated with Sufentanil

    Directory of Open Access Journals (Sweden)

    Angélica de Fátima de Assunção Braga

    2009-06-01

    étrica.BACKGROUND AND OBJECTIVES: Epidural 0.5% racemic bupivacaine associated with opioids is a technique used in cesarean sections; however, its toxicity has been questioned. 50% Enantiomeric excess bupivacaine has lower cardio- and neurotoxicity. The efficacy of epidural 0.5% racemic bupivacaine and 0.5% enantiomeric excess bupivacaine associated with sufentanil in parturients undergoing cesarean sections was evaluated. METHODS: Fifty gravida at term, undergoing elective cesarean section under epidural block, were divided in two groups according to the local anesthetic used: Group I - 0.5% racemic bupivacaine with vasoconstrictor; and Group II - 0.5% enantiomeric excess bupivacaine (S75-R25 with vasoconstrictor. In both groups, the local anesthetic (100 mg was associated with sufentanil (20 µg, and a total of 24 mL of the solution was used. The following parameters were evaluated: latency of the sensitive blockade; maximal level of the sensitive blockade; degree for motor blockade; time of motor blockade regression; duration of analgesia; maternal side effects; and neonatal repercussions. RESULTS: Latency, maximal level of sensitive blockade, degree of motor blockade, and duration of analgesia were similar in both groups; the mean time for regression of the motor blockade was significantly smaller in Group II. The incidence of side effects was similar in both groups. Maternal cardiocirculatory changes and neonatal repercussions were not observed. CONCLUSIONS: Epidural racemic bupivacaine and 50% enantiomeric excess bupivacaine provided adequate anesthesia for cesarean sections. 50% Enantiomeric excess bupivacaine is a promising alternative for this procedure, since it has faster regression of the motor blockade, which is desirable in obstetric patients.

  15. APA2[Zn3(HPO44(H2O2], a Layered Zincophosphate Featuring Template-to-Framework N–H⋯O and “Synergic” Framework-to-Template O–H⋯N Hydrogen Bonds and C–H⋯O Interactions (APA = 2-Amino-1-phenyleneammonium, C6H9N2+

    Directory of Open Access Journals (Sweden)

    Joel C. Aughey

    2012-08-01

    Full Text Available The crystal structure of APA2[Zn3(HPO44(H2O2] (APA = 2-amino-1-phenylene-ammonium, C6H9N2+ (1, as prepared by a predominantly non-aqueous synthesis, is described and compared to related compounds. 1 is built up from an alternating array of ZnO4 and HPO4 tetrahedra sharing vertices as Zn–O–P bonds to generate infinite anionic sheets. Within these sheets, polyhedral 4-, 6- and 8-rings are apparent. The negative charge of the inorganic layer is balanced by singly-protonated APA template cations and water molecules are also present. The components are linked by Nt–H⋯Of, Of–H⋯Ow, Ow–H⋯Of and Of–H⋯Nt (t = template, f = framework, w = water hydrogen bonds: the last of these represents an unusual framework-to-template interaction. Weak Ct–H⋯Of links may also play a role in consolidating the structure. Crystal data: 1 (C12H26N4O18P4Zn3, Mr = 834.36, monoclinic, C2/c (No. 15, Z = 4, a = 20.194 (8 Å, b = 8.682 (3 Å, c = 15.123 (6 Å, β = 91.510 (11°, V = 2650.5 (17 Å3, R(F = 0.048, wR(F2 = 0.112.

  16. Bupivacaína racêmica a 0,5% e mistura com excesso enantiomérico de 50% (S75-R25 a 0,5% no bloqueio do plexo braquial para cirurgia ortopédica. Estudo comparativo Bupivacaína racémica a 0,5% y mezcla con exceso enantiomérico del 50% (S75-R25 a 0,5% en el bloqueo del plexo braquial para cirugía ortopédica. Estudio comparativo Comparative study of 0.5% racemic bupivacaine versus enantiomeric mixture (S75-R25 of 0.5% bupivacaine in brachial plexus block for orthopedic surgery

    Directory of Open Access Journals (Sweden)

    Roberto Tsuneo Cervato Sato

    2005-04-01

    segura y efectiva para el bloqueo del plexo braquial para cirugía ortopédica de miembro superior.BACKGROUND AND OBJECTIVES: Several studies were performed with bupivacaine isomers in the attempt to find a safer drug than racemic bupivacaine. This study aimed at evaluating the efficacy of 0.5% bupivacaine enantiomeric mixture (MEE50% as compared to 0.5% racemic bupivacaine in brachial plexus block for upper limb orthopedic surgery. METHODS: Participated of this randomized double-blind study 40 patients aged 18 to 90 years, physical status ASA I and II, submitted to upper limb orthopedic surgeries, who were divided in two groups: Group R received 0.5% racemic bupivacaine; and Group L received 0.5% enantiomeric mixture (S75-R25 of bupivacaine both with 1:200,000 epinephrine, in a volume of 0.6 mL.kg-1 (3 mg.kg-1, limited to 40 mL. Motor and/or sensory characteristics of each nerve involved (musculocutaneous, radial, median, ulnar and medial cutaneous nerve of forearm, as well as the incidence of side effects were evaluated. RESULTS: There were no statistical differences in demographics. Hemodynamic parameters were similar between groups but systolic pressure was higher for Group R. There were no statistically significant differences in time to reach the greatest intensity of sensory and motor blocks. With one exception, the onset of motor block within the muscles innervated by the ulnar nerve was longer for Group L (10.75 versus 14.25 minutes. CONCLUSIONS: There were adequate sensory and motor blocks in both groups, with few side effects, suggesting that the 0.5% enantiomeric mixture (S75-R25 of bupivacaine with epinephrine is safe and effective for brachial plexus block of upper limb orthopedic surgeries.

  17. Fine refinement of solid state structure of racemic form of phospho-tyrosine employing NMR Crystallography approach.

    Science.gov (United States)

    Paluch, Piotr; Pawlak, Tomasz; Oszajca, Marcin; Lasocha, Wieslaw; Potrzebowski, Marek J

    2015-02-01

    We present step by step facets important in NMR Crystallography strategy employing O-phospho-dl-tyrosine as model sample. The significance of three major techniques being components of this approach: solid state NMR (SS NMR), X-ray diffraction of powdered sample (PXRD) and theoretical calculations (Gauge Invariant Projector Augmented Wave; GIPAW) is discussed. Each experimental technique provides different set of structural constraints. From the PXRD measurement the size of the unit cell, space group and roughly refined molecular structure are established. SS NMR provides information about content of crystallographic asymmetric unit, local geometry, molecular motion in the crystal lattice and hydrogen bonding pattern. GIPAW calculations are employed for validation of quality of elucidation and fine refinement of structure. Crystal and molecular structure of O-phospho-dl-tyrosine solved by NMR Crystallography is deposited at Cambridge Crystallographic Data Center under number CCDC 1005924.

  18. Configuration and racemization determination of cysteine residues in peptides by chiral derivatization and HPLC: application to oxytocin peptides.

    Science.gov (United States)

    Szabó, S; Szókán, G; Khlafulla, A M; Almás, M; Kiss, C; Rill, A; Schön, I

    2001-06-01

    An improved RP-HPLC method was developed for the determination of the configuration and stereochemical purity of cysteine residues in peptides. The method consists of oxidation of cysteine and cystine residues to cysteic acid, followed by hydrolysis and pre-column chiral derivatization with Val-Marfey's reagent.

  19. Physiological state of life in the buried biosphere: insights from amino acid racemization modeling and superresolution microscopy

    DEFF Research Database (Denmark)

    Braun, Stefan

    2016-01-01

    gener- ation times of ultra-slow microbial life from millennial toward decadal time scales. The obtained data will therefore influence our view of microbial activities on global element cycling over geologic time scales. Controlling factors of the microbial community size and its activity seemed...

  20. Lack of influence of CYP2D6 genotype on the clearance of (R)-, (S)- and racemic-methadone

    DEFF Research Database (Denmark)

    Coller, J K; Joergensen, C; Foster, D J R

    2007-01-01

    OBJECTIVE: To investigate the influence of CYP2D6 genotype on the oral clearance of (R)-, (S)- and rac-methadone. METHODS: In this retrospective study, CYP2D6 genotypes were identified in 56 methadone maintained subjects. Plasma concentrations of (R)-, (S)- and rac-methadone were determined...... by stereoselective HPLC and sufficient data were available to estimate the apparent oral clearances of (R)-, (S)- and rac-methadone using a population kinetic model in 37 of the genotyped subjects. RESULTS: The CYP2D6 allele frequencies were similar to those previously reported in Caucasians, the most common being......: CYP2D6*1 (35.2%), CYP2D6*2 (12.0%) and CYP2D6*4 (22.2%). Three unknown SNPs were found in four subjects: 1811G > A (n = 1), 1834C > T (n = 1) and 2720G > C (n = 2). The oral clearances of (R)-, (S)- and rac-methadone varied 5.4-, 6.8- and 6.1-fold, respectively. No significant differences in methadone...

  1. A New Method of Resolution of Racemic 6,6'-Dihydroxy-5,5'- biquinoline Using (S)-( + )-Camphorsulfonyl Chloride

    Institute of Scientific and Technical Information of China (English)

    CHEN Yi-Xin; LIU Tian-Sui; LIU Ru-Feng

    2003-01-01

    @@ The chiral ligand bearing C2-symmetric binaphthyl backbonce (e. g. BINOL, BINAP) is one of the widely used chiral auxiliaries in catalytic asymmetric synthesis. [1] Numerous synthetic approaches to these two compounds have been developed. In contrast, the C2-symmetric ligands containing heterocyclic moiety has been relatively less explored.

  2. Separation of racemic mixture by ultrafiltration of enantioselective micelles. 1 Effect of pH on separation and regeneration

    NARCIS (Netherlands)

    Overdevest, P.E.M.; Bruin, de T.J.M.; Riet, van 't K.; Keurentjes, J.T.F.; Padt, van der A.

    2001-01-01

    Many enantiomer separation systems are studied to meet the increasing demand for enantiopure compounds. One way to obtain pure enantiomers is to apply enantioselective micelles in ultrafiltration systems. We have studied the separation of phenylalanine (Phe) enantiomers by the ultrafiltration of non

  3. "On-the-fly" kinetics of enzymatic racemization using deuterium NMR in DNA-based chiral oriented media.

    Science.gov (United States)

    Chan-Huot, Monique; Lesot, Philippe; Pelupessy, Philippe; Duma, Luminita; Bodenhausen, Geoffrey; Duchambon, Patricia; Toney, Michael D; Reddy, U Venkateswara; Suryaprakash, N

    2013-05-07

    We report the in situ and real-time monitoring of the interconversion of L- and D-alanine-d3 by alanine racemase from Bacillus stearothermophilus directly observed by (2)H NMR spectroscopy in anisotropic phase. The enantiomers are distinguished by the difference of their (2)H quadrupolar splittings in a chiral liquid crystal containing short DNA fragments. The proof-of-principle, the reliability, and the robustness of this new method is demonstrated by the determination of the turnover rates of the enzyme using the Michaelis-Menten model.

  4. Enantioseparation of racemic trans-δ-viniferin using high speed counter-current chromatography based on induced circular dichroism technology.

    Science.gov (United States)

    Han, Chao; Xu, Jinfang; Wang, Xiaobing; Xu, Xiaoming; Luo, Jianguang; Kong, Lingyi

    2014-01-10

    A preparative chiral high speed counter-current chromatography (HSCCC) method based on induced circular dichroism (ICD) spectrum was developed to separate trans-δ-viniferin (TVN) enantiomers successfully. The important parameters for the chiral HSCCC separation process, including the type of chiral selector (CS), the concentration of chiral selector and the equilibrium temperature, were optimized using induced circular dichroism spectrum. The final separation procedure was established with a biphasic solvent system composed of n-hexane-ethyl acetate-25 mmol L(-1) hydroxypropyl-β-cyclodextrin aqueous solution (5:5:10, v/v/v) in the head-to-tail elution mode at 5 °C. Under optimum chiral HSCCC separation conditions, 8.2mg of (7S, 8S)-TVN (1) and 9.4 mg of (7R, 8R)-TVN (2) were successfully separated from 20mg TVN enantiomers with the purity of 99.51% and 99.36%, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Reverse-phase HPLC separation of D-amygdalin and neoamygdalin and optimum conditions for inhibition of racemization of amygdalin.

    Science.gov (United States)

    Hwang, Eun-Young; Lee, Je-Hyun; Lee, Yong-Moon; Hong, Seon-Pyo

    2002-10-01

    In boiling aqueous solution, D-amygdalin usually begins to convert into neoamygdalin in 3 min and more than 30% of the initial D-amygdalin is found as neoamygdalin after 30 min. In this report, we establish methods for simple HPLC analysis and the inhibition of D-amygdalin conversion. D-Amygdalin and its conversion product, neoamygdalin, were clearly separated on reverse-phase column chromatography by an optimized eluent of 10 mM sodium phosphate buffer (pH 3.8) containing 6% acetonitrile. Linearity for analyzing D-amygdalin and neoamygdalin was observed in the range from 0.05 to 0.5 mM. The detection limits for D-amygdalin and neoamygdalin were ca. 5 microM per injected amount. We found that D-amygdalin conversion was completely inhibited by adding 0.05% citric acid to the aqueous solution before boiling. To prevent the loss of pharmaceutical potency of Tonin, we applied this method to measure the conversion rate of D-amygdalin. We confirmed that D-amygdalin conversion in Tonin is effectively inhibited by acidic boiling solution with 0.1% citric acid.

  6. Sistemas de liberação controlada com bupivacaína racêmica (S50-R50 e mistura enantiomérica de bupivacaína (S75-R25: efeitos da complexação com ciclodextrinas no bloqueio do nervo ciático em camundongos Sistemas de liberación controlada con bupivacaína racémica (S50-R50 y mescla enantiomérica de bupivacaína (S75-R25: efectos de la complexación con ciclodextrinas en el bloqueo del nervio ciático en ratones Drug-delivery systems for racemic bupivacaine (S50-R50 and bupivacaine enantiomeric mixture (S75-R25: cyclodextrins complexation effects on sciatic nerve blockade in mice

    Directory of Open Access Journals (Sweden)

    Daniele Ribeiro de Araújo

    2005-06-01

    , characterizing and evaluating the anesthetic efficacy of inclusion complexes of bupivacaine enantiomeric mixture (S75-R25 and racemic bupivacaine (S50-R50 with hydroxypropylb- cyclodextrin (HPb-CD comparing them to clinically available preparations. METHODS: Inclusion complexes were obtained by mixing appropriate volumes of HPb-CD and S50-R50 or S75-R25 to final 1:1 or 1:2 molar ratios and were characterized by phase solubility experiments. Affinity constants (K were determined between HPb-CD and each LA. Motor and sensory blocks induced by plain or complexed LA formulations were evaluated in mice by sciatic nerve block. Three LA concentrations were used during the experiment: 0.125, 0.25 and 0.5%. RESULTS: Solubility experiments results were indicative of S50-R50:HPb-CD and S75-R25:HPb-CD complexation, with similar affinity constant (K values: 14.7 M-1 and 14,3 M-1, respectively. In vivo experiments have shown that complexation has enhanced differential nerve blockade induced by LA: i motor blockade duration induced by S75-R25 was similar, to the induced by but less intense S50-R50 ( p < 0.001. S50-R50HPb-CD and S75-R25HPb-CD complexes have decreased onset (p < 0.01 and p < 0.05, respectively, without changing motor block intensity (Emax as compared to plain drugs; ii sensory block evaluation has revealed higher analgesic intensity with S50-R50HPb-CD (2-fold, p < 0.001 and S75-R25HPb-CD (1.5-1.8-fold, p < 0.01 and p < 0.001, respectively with both molar ratios (1:1 and 1:2, LA:CD, in addition to prolonging analgesic effect as compared to S50-R50 and S75-R25. CONCLUSIONS: More pronounced analgesic effects obtained by complexation with HPb-CD have shown that both formulations, S50-R50HPb-CD and S75-R25HPb-CD, are very useful for postoperative pain relief, requiring lower LA concentrations. Nevertheless, it is worth noticing that S75-R25 - being less toxic than racemic bupivacaine - is an interesting alternative for the development of more effective and safe drug-delivery systems

  7. Comparação entre os efeitos hemodinâmicos da intoxicação aguda com bupivacaína racêmica e a mistura com excesso enatiomérico de 50% (S75-R25: estudo experimental em cães Comparación entre los efectos hemodinámicos de la intoxicación aguda con bupivacaína racémica y la mezcla con exceso enatiomérico de 50% (S75-R25: estudio experimental en perros Comparison of the hemodynamic effects in acute intoxication with racemic bupivacaine and with 50% enantiomeric excess mixture (S75-R25: an experimental study in dogs

    Directory of Open Access Journals (Sweden)

    Artur Udelsmann

    2006-08-01

    anestesia proporcionada. Su toxicidad cardiovascular, sin embargo ya hace mucho tiempo preocupa a los anestesiólogos y nuevas opciones han sido buscadas. Una de ellas es la utilización de su isómero levógiro que por una menor afinidad con los receptores de los canales de sodio de la célula cardiaca que sería menos cardiotóxico. En nuestro medio existe la presentación que contiene un 75% del isómero levógiro y 25% del isómero dextrógiro, denominada mezcla con exceso enantiomérico de 50% (S75-R25. El objetivo de este estudio fue comparar en animales los efectos hemodinámicos de la intoxicación aguda con bupivacaína racémica y con la mezcla S75-R25. MÉTODO: Cuarenta y cuatro perros fueron anestesiados con pentobarbital, entubados y ventilados mecánicamente, siendo en seguida instalada la monitorización hemodinámica con catéter de Swan-Ganz y presión invasiva. Después del período de reposo fueron divididos aleatoriamente en dos grupos de estudio encubierto, según la intoxicación con uno u otro agente en la dosis de 5 mg.kg-1. Los resultados hemodinámicos se recolectaron durante 30 minutos, tratados estadísticamente permitiendo la comparación de la acción de los dos agentes. RESULTADOS: La mezcla S75-R25 causó mayores repercusiones hemodinámicas, particularmente, con importante disminución de la presión arterial promedio, del índice cardiaco y del índice de trabajo del ventrículo izquierdo. CONCLUSIONES: Esos resultados se contraponen con los encontrados en humanos, cuando se utiliza el isómero levógiro puro, pero están de acuerdo con estudios recientes en animales. Rebasar datos obtenidos en animales para seres humanos exige mucha cautela. Nuevos estudios se hacen necesarios en muestras más abarcadoras y en grupos más homogéneos.BACKGROUND AND OBJECTIVES: Racemic bupivacaine has been widely used in locoregional anesthesia due to the quality and duration of its anesthetic action. However, its cardiovascular toxicity has worried

  8. Rationally re-designed mutation of NAD-independent l-lactate dehydrogenase: high optical resolution of racemic mandelic acid by the engineered Escherichia coli

    Directory of Open Access Journals (Sweden)

    Jiang Tianyi

    2012-11-01

    Full Text Available Abstract Background NAD-independent l-lactate dehydrogenase (l-iLDH from Pseudomonas stutzeri SDM can potentially be used for the kinetic resolution of small aliphatic 2-hydroxycarboxylic acids. However, this enzyme showed rather low activity towards aromatic 2-hydroxycarboxylic acids. Results Val-108 of l-iLDH was changed to Ala by rationally site-directed mutagenesis. The l-iLDH mutant exhibited much higher activity than wide-type l-iLDH towards l-mandelate, an aromatic 2-hydroxycarboxylic acid. Using the engineered Escherichia coli expressing the mutant l-iLDH as a biocatalyst, 40 g·L-1 of dl-mandelic acid was converted to 20.1 g·L-1 of d-mandelic acid (enantiomeric purity higher than 99.5% and 19.3 g·L-1 of benzoylformic acid. Conclusions A new biocatalyst with high catalytic efficiency toward an unnatural substrate was constructed by rationally re-design mutagenesis. Two building block intermediates (optically pure d-mandelic acid and benzoylformic acid were efficiently produced by the one-pot biotransformation system.

  9. Racemic but tropos (chirally flexible) BIPHEP ligands for Rh(I)-complexes: highly enantioselective ene-type cyclization of 1,6-enynes.

    Science.gov (United States)

    Mikami, Koichi; Kataoka, Shohei; Yusa, Yukinori; Aikawa, Kohsuke

    2004-10-14

    [reaction: see text] The tropos (chirally flexible) or atropos (chirally rigid) nature of BIPHEP-Rh complexes at room temperature critically depends on the amines complexed. The aliphatic DPEN complex is atropos, whereas the aromatic DABN complex is tropos. BIPHEP-Rh chirality can thus be controlled by DABN at room temperature. The amine-free BIPHEP-Rh complex is tropos. At 5 degrees C, even amine-free BIPHEP-Rh complexes are atropos and hence can be used as enantiopure catalysts to give high enantioselectivity in ene-type cyclization of 1,6-enynes.

  10. Factors relevant to the production of (R)-(+)-glycidol (2,3-epoxy-1-propanol) from racemic glycidol by enantioselective oxidation with Acetobacter pasteurianus ATCC 12874.

    Science.gov (United States)

    Geerlof, A; Jongejan, J A; van Dooren, T J; Racemakers-Franken, P C; van den Tweel, W J; Duine, J A

    1994-12-01

    Acetobacter pasteurianus oxidizes glycidol with high activity, comparable to the oxidation of ethanol. The organism has a preference for the S-enantiomer, and the kinetic resolution process obeys a simple relationship, indicating an enantiomeric ratio (E) of 19. The compound is converted into glycidic acid, although a transient accumulation of glycidaldehyde occurs initially. Determination of other parameters revealed a temperature optimum of 50 degrees C, long-term stability (cells in the resting state), and a pH optimum compatible with the chemical stability of glycidol. However, it was also noted that respiration rates decrease at concentrations of glycidol above 1 M. This is most likely caused by substrate inhibition of the glycidol-oxidizing enzyme, the quinohemoprotein ethanol dehydrogenase. Comparison with existing methods for enantiomerically pure glycidol production indicated a number of attractive points for the method described here, although definitive evaluation must await further studies on the long-term stability under process conditions, reusability of the cells, and the mechanism of glycidol inhibition.

  11. Suitability of teicoplanin-aglycone bonded stationary phase for simulated moving bed enantio separation of racemic amino acids employing composition-constrained eluents

    NARCIS (Netherlands)

    Bechtold, M; Heinemann, M; Panke, S

    2006-01-01

    The suitability of a teicoplanin-aglycone based chiral stationary phase for the simulated moving bed (SMB) enantioseparation of amino acids under enzyme-compatible conditions was shown following a procedure that is based solely on model-based simulations and HPLC experiments. A set of eight amino ac

  12. Racemic (RSC,SRS-(2-{[1-allyloxycarbonyl-3-(methylsulfanylpropyl]iminomethyl}phenyl-κ3S,N,C1chloridoplatinum(II

    Directory of Open Access Journals (Sweden)

    Katsuhiro Isozaki

    2009-11-01

    Full Text Available The title compound, [Pt(C15H18NO2SCl], was obtained by the cyclometallation reaction of cis-bis(benzonitriledichloridoplatinum(II with N-benzylidene-l-methionine allyl ester in refluxing toluene. The PtII atom has a square-planar geometry and is tetra-coordinated by the Cl atom and the C, N and S atoms from the benzylidene methionine ester ligand. In the crystal structure, the S atoms show opposite chiral configurations with respect to the α-carbon of the methionine, reducing steric repulsion between the methyl and allyl ester groups.

  13. Screening, Molecular Cloning, and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β-Hydroxy-β-trifluoromethyl Ketone.

    Science.gov (United States)

    Bulut, Dalia; Duangdee, Nongnaphat; Gröger, Harald; Berkessel, Albrecht; Hummel, Werner

    2016-07-15

    The stereoselective synthesis of chiral 1,3-diols with the aid of biocatalysts is an attractive tool in organic chemistry. Besides the reduction of diketones, an alternative approach consists of the stereoselective reduction of β-hydroxy ketones (aldols). Thus, we screened for an alcohol dehydrogenase (ADH) that would selectively reduce a β-hydroxy-β-trifluoromethyl ketone. One potential starting material for this process is readily available by aldol addition of acetone to 2,2,2-trifluoroacetophenone. Over 200 strains were screened, and only a few yeast strains showed stereoselective reduction activities. The enzyme responsible for the reduction of the β-hydroxy-β-trifluoromethyl ketone was identified after purification and subsequent MALDI-TOF mass spectrometric analysis. As a result, a new NADP(+) -dependent ADH from Pichia pastoris (PPADH) was identified and confirmed to be capable of stereospecific and diastereoselective reduction of the β-hydroxy-β-trifluoromethyl ketone to its corresponding 1,3-diol. The gene encoding PPADH was cloned and heterologously expressed in Escherichia coli BL21(DE3). To determine the influence of an N- or C-terminal His-tag fusion, three different recombinant plasmids were constructed. Interestingly, the variant with the N-terminal His-tag showed the highest activity; consequently, this variant was purified and characterized. Kinetic parameters and the dependency of activity on pH and temperature were determined. PPADH shows a substrate preference for the reduction of linear and branched aliphatic aldehydes. Surprisingly, the enzyme shows no comparable activity towards ketones other than the β-hydroxy-β-trifluoromethyl ketone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Applications of amino acid racemization thermometry in earth science%氨基酸外消旋测温法在地学中的应用

    Institute of Scientific and Technical Information of China (English)

    洪华华; 王将克; 钟月明

    1986-01-01

    @@ 地质学家,尤其是古地理工作者对于不同地质时期的古气候变化情况特别关注.不同地质时期的气候变化直接影响到生物群的变化,也影响到动物的迁移、海面的扩涨或退缩、地壳岩石的物理及化学风化作用等等.地质时期气候的变化也是划分和对比第四纪地层的一种重要依据,而古温度又是古气候中的一个重要指标,所以,古温度的确定已成为地学研究中的一个重要组成部分.

  15. Baeyer-Villiger monooxygenase-catalyzed kinetic resolution of racemic alpha-alkyl benzyl ketones : enzymatic synthesis of alpha-alkyl benzylketones and alpha-alkyl benzylesters

    NARCIS (Netherlands)

    Rodriguez, Cristina; de Gonzalo, Gonzalo; Pazmino, Daniel E. Torres; Fraaije, Marco W.; Gotor, Vicente

    2009-01-01

    The application of three BVMOs for the enantioselective oxidation of 3-phenylbutan-2-ones with different substituents in the aromatic moiety is described. By choosing the appropriate biocatalyst and substrate combination, chiral ketones and esters can be obtained with excellent enantiopurities. This

  16. Synthesis of the racemate and individual enantiomers of [[sup 11]C]methylphenidate for studying presynaptic dopaminergic neutron with positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Y.-S.; Sugano, Y.; Fowler, J.S.; Salata, C. (Brookhaven National Lab., Upton, NY (United States))

    1994-10-01

    Carbon-11 labeled dl-threo-methylphenidate (methyl-2-phenyl-2-(2-piperidyl)acetate, Ritalin), a psychostimulant drug widely used to treat attention deficit hyperactivity disorder, was prepared in two steps: O-methylation of the N-protected dl-threo-ritalinic acid derivative with [[sup 11]C]methyl iodide followed by deprotection. The same strategy was applied for the preparation of C-11 labeled individual enantiomers of threo-methylphenidate from N-protected d-threo-l-threo-ritalinic acid. The subsequent C18 sep-pak and reverse-phase HPLC purification resulted in ca. 40% radiochemical yield with a total synthesis time of 40 minutes and an average specific activity of 1.5 Ci/[mu]mole (at EOB). (author).

  17. 分子印迹聚合物拆分消旋体酮洛芬%Separation of racemic ketoprofen by molecularly imprinted polymer

    Institute of Scientific and Technical Information of China (English)

    姜吉刚; 任建成; 许丽晓; 王怀友

    2004-01-01

    以(S)-酮洛芬为印迹分子利用分子印迹技术合成能识别(S)-酮洛芬的聚合物.聚合物作为高效液相色谱的固定相,消旋体酮洛芬在固定相能分开,同时聚合物还能将酮洛芬和布洛芬的混合物分开.

  18. Racemic tricarbonyl[(4a,5,6,7,8,8a-η-2-phenyl-3,4-dihydro-2H-1-benzopyran]chromium(0

    Directory of Open Access Journals (Sweden)

    Johannes H. van Tonder

    2010-09-01

    Full Text Available The title compound, [Cr(C15H14O(CO3], displays a distorted envelope configuration of the dihydropyrane ring. The dihedral angle between the phenyl and phenylene rings is 50.63 (4°. The Cr0 atom is coordinated by three CO groups and the phenylene ring of the flavan ligand in an η6 mode, with a common arene-to-metal distance

  19. 苯丙氨酸光学异构体的酶法拆分%Aminoacylase Catalyzed Optical Resolution of Phenylalanine Racemate

    Institute of Scientific and Technical Information of China (English)

    姜忠义; 陈洪钫

    2001-01-01

    The L-phenylalanine was prepared in high optical purity bytreating N-acetylphenylalanine ethyl ester in water or in water-octanol biphase medium using free aminoacylase as a catalyst. The kinetic behavior of the free enzymatic reaction was investigated and the reaction mechanism has been discussed.

  20. Chiral ligand-exchange high-performance liquid chromatography with copper (II)-L-phenylalanine complexes for separation of 3,4-dimethoxy-α-methylphenylalanine racemes.

    Science.gov (United States)

    Jia, Dong-Xu; Ai, Zheng-Gui; Xue, Ya-Ping; Zheng, Yu-Guo

    2014-11-01

    L-3, 4-dimethoxy-α-methylphenylalanine (L-DMMD) is an important intermediate for the synthesis of 3-hydroxy-α-methyl-L-tyrosine (L-methyldopa). This paper describes an efficient, accurate, and low-priced method of high-performance liquid chromatography (HPLC) using chiral mobile phase and conventional C18 column to separate L-DMMD from its enantiomers. The effects of ligands, copper salts, organic modifiers, pHs of mobile phase, and temperatures on the retention factors (k') and selectivity (α) were evaluated to achieve optimal separation performance. Then, thermal analysis of the optimal separation conditions was investigated as well. It was confirmed that the optimal mobile phase was composed of 20 % (v/v) methanol, 8 mM L-phenylalanine (L-Phe), and 4 mM cupric sulfate in water of pH 3.2, and the column temperature was set at 20 °C. Baseline separation of two enantiomers could be obtained through the conventional C18 column with a resolution (R) of 3.18 in less than 18 min. Thermodynamic data (∆∆H and ∆∆S) obtained by Van't Hoff plots revealed the chiral separation was an enthalpy-controlled process. To the best of our knowledge, this is the first report regarding the enantioseparation of DMMD by chiral ligand-exchange HPLC.

  1. Design and synthesis of novel imidazolium-based ionic liquids with a pseudo crown-ether moiety: diastereomeric interaction of a racemic ionic liquid with enantiopure europium complexes

    OpenAIRE

    2004-01-01

    A planar-chiral imidazolium salt with a tris(oxoethylene) bridge was synthesized, and its potential application as a room-temperature ionic liquid with a molecular-recognition ability was demonstrated.

  2. 云杉红翅小蠹信息素Seudenone和(±)-Seudenol的简便合成%A Facile Synthesis of Seudenone and Racemic Seudenol

    Institute of Scientific and Technical Information of China (English)

    殷彩霞; 高竹林; 刘复初; 李霁良; 张甦

    2000-01-01

    Seudenone (3-methylcyclohex-2-en-1-one) is an antiaggregation pheromone of Douglas fir beetle,Dendroctonus pseudotsugae.Seudenol (3-methyl cyclohex-2-en-1-ol) is an aggregation pheromone of Douglas fir beetle,Dendroctonus pseudotsugae.The synthesis employed ethyl acetoacetate and paraformaldehyde as starting materials.The route of synthesis was carried out by 3 steps:condensation,hydrolysis and decaxboxylation,and regioselective reduction.%3-甲基环己-2-烯-1-酮(Seudenone)是云杉红翅小蠹的抑制信息素,3-甲基环己-2-烯-1-醇(±-Seudenol)却是一种聚集信息素.本合成利用乙酰乙酸乙酯和多聚甲醛为原料,通过缩合、水解脱羧和区域选择性还原三步反应合成了两个所需产物.

  3. Racemization at C-2 of naringin in pummelo (Citrus grandis) with increasing maturity determined by chiral high-performance liquid chromatography.

    Science.gov (United States)

    Caccamese, Salvatore; Chillemi, Rosa

    2010-02-12

    The relative content of (2S)- and (2R)-naringin in the albedo of pummelo during maturation in the entire season was determined by normal-phase HPLC using Chiralpak IB, a polysaccharide-derived chiral stationary phase, and n-hexane/ethanol doped with 0.5% TFA as mobile phase. A sigmoid curve was obtained showing variation from 95.3% of (2S)-naringin in very immature fruits to 53% in mature fruit samples (2.3 and 14.4cm diameter, respectively). A comparison was made with previous results obtained for grapefruit and sour orange and a tentative explanation of the bitter taste of sour orange is proposed. The Chiralpak IB is much more efficient with respect to the Chiralcel OD used for the other two Citrus species and separation and resolution factors of 1.73 and 9.2, respectively, were achieved. Authentic samples of naringin and neohesperidin were also separated into their C-2 diastereomers with Chiralpak IB and isolation of the pure diastereomers of naringin was accomplished.

  4. Synthesis and modification of mesoporous silica and the preparation of molecular sieve thin films via pulsed laser deposition

    Science.gov (United States)

    Coutinho, Decio Heringer

    2001-07-01

    Hexagonal mesoporous DAM-1 (Dallas Amorphous Material-1) was prepared using Vitamin E TPGS as the structure-directing agent. Depending upon the temperature and gel composition, highly ordered and hydrothermally stable DAM-1 with various morphologies could be achieved including spheres, gyroids, discoid, hexagonal plates and rods. This synthesis was modified to prepare hybrid organic-inorganic amine and thiol bifunctionalized DAM-1 by direct co-condensation under acidic conditions. Patterned DAM-1 thin films were prepared on patterned transparencies utilizing pulsed laser deposition (PLD) and line patterning techniques. DAM-1 laser ablation onto the patterned substrate followed by hydrothermal treatment resulted in a densely packed film. Removal of the patterned lines by sonication revealed patterned DAM-1 films. Thin films of zeolite type X were also prepared using the PLD technique. Laser ablation of zeolite X onto TiN-coated silicon wafers followed by a hydrothermal treatment resulted in partially oriented, crystalline membranes. Hydrothermal treatment of PLD films on stainless steel mesh produced a coated wire mesh with a 3-mum thick zeolite X film. A novel strategy for imprinting mesoporous SBA-15 that combines a triblock copolymer template and a chiral ruthenium complex is reported. A chiral PEO helix was formed by the chiral ruthenium complex interaction with the block copolymer during the synthesis of SBA-15. Upon removal of the chiral ruthenium complex, a stereospecfic cavity was created. Preliminary results indicated stereoselective absorption of Delta or Λ-Ru(phen)3 2+ isomer from a racemic mixture could be achieved depending on the chirality of the PEO chain. Practicum Two. The industrial practicum report describes the process development unit (PDU) 3-pentenenitrile (3PN) refining operation. This distillation works was operated to refine crude 3PN product, which contained 3PN, 2-methyl-3-butenenitrile (2M3BN), and other byproducts. This report also

  5. Comparação das alterações histológicas da medula espinal e neurológicas de cobaias após anestesia subaracnóidea com grandes volumes de bupivacaína racêmica, de mistura com excesso enantiomérico de 50% de bupivacaína (S75-R25 e de levobupivacaína Comparación de las alteraciones histológicas de la medula espinal y neurológicas de hámsteres después de la anestesia subaracnoidea con grandes volúmenes de bupivacaina racémica, de mezcla con exceso enantiomérico de 50% de bupivacaína (S75-R25 y de levobupivacaína Comparison of histologic spinal cord and neurologic changes in guinea pigs after subarachnoid block with large volumes of racemic bupivacaine, 50% enantiomeric excess bupivacaine (S75-R25, and levobupivacaine

    Directory of Open Access Journals (Sweden)

    Paulo de Oliveira Vasconcelos Filho

    2008-06-01

    central, si los comparamos con los inducidos por la bupivacaína racémica, sin embargo el efecto anestésico es menos intenso. Fue realizado un estudio experimental para comparar efectos adversos de grandes volúmenes de bupivacaína, de bupivacaína S75-R25 y de levobupivacaína cuando se inyectaron en el espacio subaracnoideo de los hámsteres. MÉTODO: Cuarenta hámsteres se dividieron en cuatro grupos. Anestesiados con O2 a 100% e isoflurano a 2%, con posterior punción en el espacio intervertebral L6-S1. En los animales del Grupo I se administraron 2 mL de solución fisiológica a 0,9%; en el Grupo II, 2 mL de bupivacaína 0,5%; en el Grupo III, 2 mL de bupivacaína S75-R25 0,5% y en el Grupo IV, 2 mL de levobupivacaína 0,5%. Después del despertar, en los momentos 0, 60, 120 y 180 minutos, fue realizado examen neurológico diariamente por una semana. Los animales fueron sacrificados y sometidos a la perfusión con paraformaldeido a 4%. Después de la fijación, la médula espinal fue aislada por disección y analizada histológicamente para evaluar el grado de lesión medular. RESULTADOS: Los hámsteres del grupo control no presentaron bloqueo nervioso. Los del Grupo II presentaron bloqueo sensitivo y motor por más de 180 minutos. En los Grupos III (S75-R25 y IV (levobupivacaína hubo un bloqueo motor y sensitivo al momento 0 minuto, sin embargo al momento 60 minutos el bloqueo motor era mínimo. En el examen histológico, el Grupo I no presentó alteraciones. En el Grupo II fueron encontradas alteraciones medulares intensas. En el Grupo III y IV las alteraciones medulares fueron poco intensas. CONCLUSIONES: La levobupivacaína en grandes volúmenes causó poco daño al sistema nervioso comparada a la bupivacaína. Entre la levobupivacaína y la bupivacaína S75-R25, no hubo diferencia estadística significativa.BACKGROUND AND OBJECTIVES: Levobupivacaine has less central nervous system side effects than racemic bupivacaine, but its anesthetic effect is not as

  6. Effect of the residual silanol group protection on the liquid chromatographic resolution of racemic primary amino compounds on a chiral stationary phase based on optically active (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6.

    Science.gov (United States)

    Hyun, Myung Ho; Han, Sang Cheol; Choi, Hee Jung; Kang, Bu Sung; Ha, Hyun Ju

    2007-01-05

    A liquid chromatographic chiral stationary phase (CSP) based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6, which has been utilized in the resolution of alpha-amino acids, amines and amino alcohols, was treated with excess of n-octyltriethoxysilane to prepare a new improved CSP. The residual silanol groups of the original CSP were protected by n-octyl groups in the new CSP. The chiral recognition ability of the new CSP was superior to that of the original CSP in the resolution of alpha-amino acids, amines and amino alcohols. Retention factors (k1) for the resolution of alpha-amino acids were lower on the new CSP than on the original CSP while those for the resolution of amines and amino alcohols were higher on the new CSP than on the original CSP. The improved chiral recognition ability of the new CSP and the retention behaviors of the two enantiomers on the new CSP have been rationalized to stem from the removal of the non-enantioselective interactions between the analytes and the residual silanol groups of the original CSP and the improved lipophilicity of the CSP.

  7. 高选择性脂肪酶的筛选及其拆分布洛芬%Screening of a Lipase with High Enantioselectivity and Its Application in the Resolution of Racemic Ibuprofen

    Institute of Scientific and Technical Information of China (English)

    郭华颖; 唐良华; 苏敏; 薛建平; 许旭萍

    2007-01-01

    为了实现脂肪酶在有机相中对外消旋布洛芬的高效拆分,筛选得到了一株具有高立体选择性的脂肪酶产生菌-扩展青霉TS414(Penicillium expansum TS414). 实验探讨了水分、温度、有机溶剂、酶浓度、醇结构和醇浓度对酶促拆分反应的影响,确立了酯化反应的最佳反应体系:布洛芬6.46 mmol/L,脂肪酶53.3 mg/mL,正丙醇40 mmol/L,异辛烷15 mL,水0.5%((φ)),60℃条件下反应50 h. 在此条件下,拆分反应的转化率和对映体选择率分别为42%和429.63. 结果表明,Penicillium expansum TS414脂肪酶是一种较为理想的用于外消旋布洛芬拆分的工具酶,在布洛芬手性拆分方面具有广阔的应用前景.

  8. 苹果酸钼外消旋体的合成、光谱性质和结构表征%Synthesis and Spectroscopic and Structural Characterization of Racemic Ammonium Dimeric(malato)dioxomolybdenum

    Institute of Scientific and Technical Information of China (English)

    颜文斌; 周朝晖; 章慧; 万惠霖; 蔡启瑞

    2001-01-01

    钼酸铵和外消旋苹果酸溶液反应得到外消旋苹果酸钼(Ⅵ)配合物, (NH4)4*, 对该配合物进行了元素分析、电导测定、旋光和红外光谱表征, 并测定了晶体结构. 该化合物晶体属单斜晶系, P21/a空间群, 晶胞参数: a=0.806 1(2) nm, b=1.328 6(2) nm, c=1.323 2(2) nm, β=91.80(2)°, V=1.416 4(9) nm3, Z=2, Dc=2.008 g*cm-3 , F(000)=864, μ=9.70 cm-1, 一致性因子R=0.051, Rw=0.058. 在该单核配合物阴离子中, 钼上的两个苹果酸配体具有相同手性, 它以α-烷氧基和α-羧基双齿配位形成畸变的八面体构型, 而另一个β-羧酸则保持自由状态.

  9. Crystal structure of racemic [(1R,2S,3R,4S,6S-2,6-bis(furan-2-yl-4-hydroxy-4-(thiophen-2-ylcyclohexane-1,3-diyl]bis(thiophen-2-ylmethanone

    Directory of Open Access Journals (Sweden)

    Ísmail Çelik

    2016-07-01

    Full Text Available In the title compound, C28H22O5S3, the central cyclohexane ring adopts a chair conformation. The atoms of the furan ring attached to the 6-position of the central cyclohexane ring are disordered over two sets of sites with occupancies of 0.832 (5 and 0.168 (5. The hydroxy group is disordered over two positions (at the 4- and 6-positions of the cyclohexane ring in the ratio 0.832 (5:0.168 (5. In the crystal, molecules are linked by C—H...O hydrogen bonds and C—H...π interactions, forming layers parallel to (100.

  10. Utilização de zeólitas sintetizadas a partir de xisto retortado na remoção de arsênio em águas contaminadas Use of zeolites synthesized from oil shale ash for arsenic removal from polluted water

    Directory of Open Access Journals (Sweden)

    Nádia Regina Camargo Fernandes-Machado

    2007-10-01

    Full Text Available The solid by-product of the oil shale processing (PETROBRAS - Brazil was used as raw material to synthesize zeolites A and faujasite. Alkaline fusion followed by hydrothermal treatment was the synthesis procedure used, and five different starting material compositions were obtained. The more crystalline zeolite-type materials synthesized, the pretreated oil shale ash and commercial zeolites were used as adsorbents in the purification of pollutant solutions with arsenic. The zeolite-type material composed of a mixture of zeolite A (42.6% and faujasite (52.9% presented an ion exchange capacity comparable to the pure zeolites A and faujasite, much better than the pretreated ash.

  11. RACIAL CONTACT, PERSONALITY, AND GROUP PROBLEM SOLVING.

    Science.gov (United States)

    ABNER, EDWARD V.; LEWIT, DAVID W.

    THIS STUDY TESTS THE HYPOTHESIS THAT BIRACIAL GROUPS IN WHICH RACEMATES WERE PAIRED FOR DIRECT CONTACT WOULD PERFORM BETTER THAN THOSE IN WHICH RACEMATES WERE ISOLATED. IT ALSO ASSUMED THAT ETHNOCENTRIC SUBJECTS WOULD PERFORM BETTER WITH CONTACT WITH A RACEMATE, AND THAT AGGRESSIVE SUBJECTS WOULD GET ALONG WELL WITHOUT IT. THE SUBJECTS WERE BOYS…

  12. Estudo comparativo entre levobupivacaína a 0,5% e bupivacaína racêmica a 0,5% associadas ao sufentanil na anestesia peridural para cesariana

    OpenAIRE

    João Batista Santos Garcia; Oliveira,José R; Silva,Elismar P A; Privado, Marcelo S; Yamashita,Américo M; Issy,Adriana M

    2001-01-01

    BACKGROUND AND OBJECTIVES: Although the widespread use of local anesthetics in surgery and obstetrics, racemic bupivacaine is associated to potentially fatal cardiotoxicity. Data suggest that levobupivacaine has local anesthetic effects similar to racemic bupivacaine with the advantage of less central nervous system and cardiovascular toxicity. Studies have shown that epidural anesthesia with racemic bupivacaine and sufentanil for cesarean sections results in a better quality of anesthesia. T...

  13. Development of safer molecules through chirality

    OpenAIRE

    Patil P; Kothekar M

    2006-01-01

    Many of the drugs currently used in medical practice are mixtures of enantiomers (racemates). Many a times, the two enantiomers differ in their pharmacokinetic and pharmacodynamic properties. Replacing existing racemates with single isomers has resulted in improved safety and/or efficacy profile of various racemates. In this review, pharmacokinetic and pharmacodynamic implications of chirality are discussed in brief, followed by an overview of some important chiral switches that have yielded ...

  14. Reinforcing effects of abused 'bath salts' constituents 3,4-methylenedioxypyrovalerone and α-pyrrolidinopentiophenone and their enantiomers.

    Science.gov (United States)

    Gannon, Brenda M; Rice, Kenner C; Collins, Gregory T

    2017-10-01

    Synthetic cathinones found in abused 'bath salts' preparations are chiral molecules. Racemic 3,4-methylenedioxypyrovalerone (MDPV) and α-pyrrolidinopentiophenone (α-PVP) are two common constituents of these preparations that have been reported to be highly effective reinforcers; however, the relative contribution of each enantiomer toward these effects has not been determined. Thus, male Sprague-Dawley rats were trained to respond for racemic MDPV or α-PVP (n=9/drug), with full dose-response curves for the racemate and the S and R enantiomers of MDPV and α-PVP generated under a progressive ratio schedule of reinforcement. Racemic mixtures of both MDPV and α-PVP as well as each enantiomer maintained responding in a dose-dependent manner, with racemic MDPV and α-PVP being equipotent. The rank order of potency within each drug was S enantiomer>racemate ≫ R enantiomer. Although both enantiomers of α-PVP were as effective as racemic α-PVP, R-MDPV was a slightly less effective reinforcer than both S and racemic MDPV. The results of these studies provide clear evidence that both enantiomers of MDPV and α-PVP function as highly effective reinforcers and likely contribute toward the abuse-related effects of 'bath salts' preparations containing racemic MDPV and/or α-PVP.

  15. A STUDY ON IDENTIFICATION METHOD OF STEM-GROWTH HABIT TYPES(SGHT)IN SOYBEAN-APICAL RACEME-1/3 THE RELATIVE VALUE OF NODE LOCATION%大豆茎生长习性分类方法的研究—茎顶花序—1/3节位相对值法

    Institute of Scientific and Technical Information of China (English)

    王晋华; 张孟臣; 盖钧镒

    2002-01-01

    本文在大豆有限、亚有限与无限型茎顶判别标记性状基础上,选用最大叶片着生节位相对值(LRV)和最长叶柄着生节位相对值(PRV)做为划分有限型与亚有限型的指标,借助次数分布(图)法和混合模型法确定1/3节位处(距茎顶)为分界点,≤0.33为有限型,>0.33为亚有限,此方法简称为茎顶花序-1/3节位相对值法(AR-LRV,AR-PRV).

  16. 扩展青霉脂肪酶的生产及其在外消旋烯丙醇酮拆分上的应用%Production of the Lipase from Penicillium expansum PED-03 and its Application in the Resolution of Racemic Allethrolone

    Institute of Scientific and Technical Information of China (English)

    戴大章; 夏黎明

    2008-01-01

    试图应用脂肪酶催化拆分法代替化学法拆分外消旋烯丙醇酮(4-羟基-3-甲基-2-(2-烯丙基)-2-环戊烯-1-酮,allethrolone).以Rodamine B平板筛选法获得了一株脂肪酶高产菌Penicillium expansum PED-03,并对该菌液态发酵产脂肪酶的主要工艺参数进行了优化.确立了0.5%的淀粉和4% 的豆饼粉为该菌种的适宜碳源和氮源,最适C/N为0.5.Tween-80对产酶有明显的促进作用,添加0.05% Tween-80后所产酶活力可提高55%.发酵罐产酶试验结果表明,搅拌速度对脂肪酶的产生有明显影响,适宜的搅拌速度为500 r·min-1. 利用P. expansum PED-03脂肪酶在非水相中对外消旋烯丙醇酮进行手性拆分,反应36 h时转化率(C)可达理论值的96%,产物的对映体过量值(eeP)可达99%,显示了该酶在烯丙醇酮的酶法拆分方面具有良好的应用潜力.的淀粉和4% 的豆饼粉为该菌种的适宜碳源和氮源,最适C/N为0.5.Tween-80对产酶有明显的促进作用,添加0.05% Tween-80后所产酶活力可提高55%.发酵罐产酶试验结果表明,搅拌速度对脂肪酶的产生有明显影响,适宜的搅拌速度为500 r·min-1. 利用P. expansum PED-03脂肪酶在非水相中对外消旋烯丙醇酮进行手性拆分,反应36 h时转化率(C)可达理论值的96%,产物的对映体过量值(eeP)可达99%,显示了该酶在烯丙醇酮的酶法拆分方面具有良好的应用潜力.

  17. Crystal structure of racemic [(1R,2S,3R,4S,6S)-2,6-bis-(furan-2-yl)-4-hy-droxy-4-(thio-phen-2-yl)cyclo-hexane-1,3-di-yl]bis-(thio-phen-2-yl-methanone).

    Science.gov (United States)

    Çelik, Ísmail; Ersanlı, Cem Cüneyt; Akkurt, Mehmet; Gezegen, Hayrettin; Köseoğlu, Rahmi

    2016-07-01

    In the title compound, C28H22O5S3, the central cyclo-hexane ring adopts a chair conformation. The atoms of the furan ring attached to the 6-position of the central cyclo-hexane ring are disordered over two sets of sites with occupancies of 0.832 (5) and 0.168 (5). The hy-droxy group is disordered over two positions (at the 4- and 6-positions of the cyclo-hexane ring) in the ratio 0.832 (5):0.168 (5). In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and C-H⋯π inter-actions, forming layers parallel to (100).

  18. Comparison of the insecticidal activities of terpinen-4-ol optical isomers and racemate against the housefly, Musca domestica%松油烯-4-醇光学异构体及外消旋体对家蝇的杀虫活性比较

    Institute of Scientific and Technical Information of China (English)

    李琳; 熊鑫; 马树杰; 马志卿; 张兴

    2015-01-01

    [目的]比较松油烯-4-醇光学异构体对家蝇Musca domestica的熏蒸活性差异,为其光学异构体的应用提供理论依据.[方法]以家蝇4日龄成虫为供试昆虫,采用三角瓶熏蒸法比较测定了松油烯-4-醇光学异构体和外消旋体对其的熏蒸与击倒活性,并测定了松油烯-4-醇光学异构体及外消旋体对家蝇头部Na+,K+-ATPase活性的影响.[结果]松油烯-4-醇外消旋体对家蝇的熏蒸活性和击倒活性最强,右旋异构体次之,左旋异构体最差,外消旋体、右旋异构体和左旋异构体对家蝇的致死中浓度(LC50)分别为2.5,2.9和3.7μL/L;在LC90剂量下的击倒中时(KT50)分别为12.6,16.7和18.9 min;松油烯-4-醇光学异构体及外消旋体均可显著抑制Na+,K+-ATPase的活性,活体条件下,松油烯-4-醇光学异构体及外消旋体对Na+,K+-ATPase活性的抑制作用随着中毒症状的加剧而增强,具有时间效应,其中左旋异构体的抑制作用最强;离体条件下,松油烯-4-醇光学异构体及外消旋体对Na+,K+-ATPase活性的抑制作用具有浓度依赖效应,其中外消旋体对Na+,K+-ATPase活性的抑制能力最强,明显高于同浓度下的右旋异构体和左旋异构体.[结论]松油烯-4-醇的光学异构体对家蝇的杀虫活性存在差异,外消旋体的活性明显高于异构体单体.开发松油烯-4-醇类杀虫剂,应以光学异构体的混合物作为有效成分.

  19. Synthesis, Crystal Structures and Characterization of Two Racemic Dual-U-Shaped Mononuclear Lanthanide Complexes%两个外消旋双U形稀土单核配合物的合成、晶体结构及其表征

    Institute of Scientific and Technical Information of China (English)

    解庆范; 黄妙龄; 陈延民

    2009-01-01

    对氨基苯磺酸(p-AbsH),邻菲咯啉(phen)与稀土硝酸盐在pH=6~7的水溶液中反应,合成了2个新颖的双U形单核配合物[Ln(O-p-Abs)2(phen)2(H2O)3]·(NO3)·2H2O,其中Ln=La(1)和Ce(2).X-射线单晶结构测定表明,2种晶体属异质同晶,正交晶系,Pccn空间群.在2个配合物中,Ln(Ⅲ)离子与5个O原子和4个N原子配位,形成1个畸变的三冠三棱柱体LnN4O5配位多面体,其中2个氧原子来自于2个对氨基苯磺酸根的磺酸基,另3个O原子则由配位水分子提供.4个N原子来自2个Phen.p-Abs与phen通过π-π作用构成具有手性的螺旋双U形结构,每个晶胞中含有2对构型相反的[Ln(O-p-Abs)2(phen)2(H2O3)+,整个晶体呈外消旋.2种异构体分子间通过phen间的π-π作用构成超分子螺旋链,并通过氢键作用形成三维超分子结构.

  20. 产碱杆菌ECU0401催化拆分扁桃酸及其衍生物%Preparation of (R)-(-)-mandelic acid and its derivatives from racemates by enantioselective degradation with strain Alcaligenes sp.ECU0401

    Institute of Scientific and Technical Information of China (English)

    何玉财; 许建和

    2009-01-01

    从土壤中分离的1株产碱杆菌Alcaligenes sp.ECU0401具有扁桃酸脱氢酶活性,可以以扁桃酸、苯甲酰甲酸或苯甲酸为唯一C源生长,并且具有较高的脱氢酶活力.以外消旋扁桃酸为C源,采用分批补料策略培养(或反应)99 h,扁桃酸累计投入量为30.4 g/L,(S)-(+)-扁桃酸被完全降解,(R)-(-)-扁桃酸回收产率为32.8%,对映体过量值(e.e.)>99.9%.利用静息细胞作为催化剂不对称降解外消旋扁桃酸的氯代衍生物,制备获得光学活性的(R)(-)邻氯扁桃酸、(S)-(+)-间氯扁桃酸和(S)-(+)-对氯扁桃酸,光学纯度均超过99.9%e.e..

  1. Ion exchange equilibrium constants

    CERN Document Server

    Marcus, Y

    2013-01-01

    Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and

  2. Nye ligander for Pt-MOF strukturer

    OpenAIRE

    Jakobsen, Søren

    2006-01-01

    Metalorganic frameworks (MOFs) are a new type of compounds which have been intensely investigated during the last few years. They have been synthesized using a wide variety of metals and ligands constructing a vast number of 1, 2 and 3 dimensional structures, some of which possess zeolite-type physics and chemistry. Our approach is to incorporate platinum metal sites into the structures making them bimetallic and potentially catalytically active. Therefore a number of N-N-type ligands (dii...

  3. Japan Report No. 171

    Science.gov (United States)

    2007-11-02

    82 14. Put into execution long-term continuous operating research on methane fermentation, thermal cracking of oil , and thermolytic gasification...vapor phase of hydrocarbons using metal family, regular structure, zeolite type, and modified zeolite catalysts . (v) Catalyst Research Common to C...previous project "new methods of producing olefins" using crude oil as the raw material; a large pilot plant of 120 tons/day capacity of raw material

  4. Inactivation of bacteria G(+)-S. aureus and G(-)-E. coli by phototoxic polythiophene incorporated in ZSM-5 zeolite.

    Science.gov (United States)

    Cík, Gabriel; Priesolová, Sona; Bujdáková, Helena; Sersen, Frantisek; Potheöová, Timea; Kristín, Jozef

    2006-06-01

    A new heterogeneous photocatalyst was prepared by oxidative polymerization of the thiophene with ferric chloride in the ZSM-5 zeolite type. The synthesized polythiophene absorbs radiation in the visible range of the electromagnetic spectrum and by illumination with visible light generates reactive oxygen species (ROS) in water medium. During illumination reactive hydroxyl radical was detected by the spin trapping EPR method. Efficiency of the photocatalyst was tested on the killing of Gram-positive bacteria Staphylococcus aureus and Gram negative bacteria Escherichia coli.

  5. Formaldehyde Adsorption into Clinoptilolite Zeolite Modified with the Addition of Rich Materials and Desorption Performance Using Microwave Heating

    Directory of Open Access Journals (Sweden)

    Amin Kalantarifard

    2016-01-01

    Full Text Available Granite, bentonite, and starch were mixed with clinoptilolite zeolite to produce a modified zeolite. The modified zeolite was tested for its ability to absorb formaldehyde from air. The modified sample formaldehyde adsorption capacity was then compared with those of commercially available clinoptilolite, faujasite (Y, mordenite, and zeolite type A. Studies were focused on the relationships between the physical characteristics of the selected zeolites (crystal structure, surface porosity, pore volume, pore size and their formaldehyde adsorption capacity. The removal of starch at high temperature (1100°C and addition of bentonite during modified clinoptilolite zeolite (M-CLZ preparation generated large pores and a higher pore distribution on the sample surface, which resulted in higher adsorption capacity. The formaldehyde adsorption capacities of M-CLZ, clinoptilolite, faujasite (Y, zeolite type A, and mordenite were determined to be 300.5, 194.5, 123.7, 106.7, and 70 mg per gram of zeolite, respectively. The M-CLZ, clinoptilolite, and faujasite (Y crystals contained both mesoporous and microporous structures, which resulted in greater adsorption, while the zeolite type A crystal showed a layered structure and lower surface porosity, which was less advantageous for formaldehyde adsorption. Furthermore, zeolite regeneration using microwave heating was investigated focusing on formaldehyde removal by desorption from the zeolite samples. XRD, XRF, N2 adsorption/desorption, and FE-SEM experiments were performed to characterize the surface structure and textural properties the zeolites selected in this study.

  6. Antimalarial activity of the bisquinoline trans-N1,N2-bis (7- chloroquinolin-4-yl)cyclohexane-1,2-diamine: Comparison of two stereoisomers and detailed evaluation of the S,S enantiomer, Ro 47-7737

    NARCIS (Netherlands)

    Ridley, R.G.; Matile, H.; Jaquet, C.; Dorn, A.; Hofheinz, W.; Leupin, W.; Masciadri, R.; Theil, F.P.; Richter, W.F.; Girometta, M.A.; Guenzi, A.; Urwyler, H.; Gocke, E.; Potthast, J.M.; Csato, M.; Thomas, A.; Peters, W.

    1997-01-01

    The S,S enantiomer of the bisquinoline trans-N1,N2-bis(7- chloroquinolin-4-yl)cyclohexane-1,2-diamine, Ro 47-7737, is significantly more potent against chloroquine-resistant Plasmodium falciparum than the R,R enantiomer and the previously described racemate. Both the enantiomers and the racemate are

  7. Synthesis of New N-Quaternary-3-benzamidoquinuclidinium Salts

    Directory of Open Access Journals (Sweden)

    Srdjanka Tomic

    2006-09-01

    Full Text Available The synthesis of racemic and enantiomerically pure N-p-methylbenzyl-3- and N-p-chlorobenzylbenzamidoquinuclidinium bromides (6-8 and 9-11, respectively is described. These compounds were prepared from racemic or enantiomerically pure 3-benzamidoquinuclidines 3-5 using the appropriate quaternization reagents: p-methyl- benzyl bromide (1 and p-chlorobenzyl bromide (2.

  8. Investigation of racemisation of the enantiomers of glitazone drug compounds at different pH using chiral HPLC and chiral CE

    DEFF Research Database (Denmark)

    Jamali, Babak; Bjørnsdottir, Inga; Nordfang, Ole;

    2008-01-01

    racemisation of the pure enantiomers is very important. In order to obtain the enantiomers of the racemic pioglitazone and the racemic rosiglitazone an HPLC method for chiral separation was developed. Using this method the R and S enantiomers were separated and the method was used to collect each enantiomer...

  9. Lipase-catalyzed hydrolysis of methyl-3-phenylglycidate

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The enzymatic resolution of racemic methyl 3-phenylglycidate was investigated. It was found that the hydrolysis rate of (2S, 3R)-enantiomer was faster than that of (2R, 3S)-enantiomer by a new lipase. At optimal condition 96% of (2R, 3S)-methyl phenylglycidate with ee of 100% was recovered from the racemic mixture.

  10. Det sorte USA

    DEFF Research Database (Denmark)

    Brøndal, Jørn

    Bogen gennemgår det sorte USAs historie fra 1776 til 2016, idet grundtemaet er spændingsforholdet mellem USAs grundlæggelsesidealer og den racemæssige praksis, et spændingsforhold som Gunnar Myrdal kaldte "det amerikanske dilemma." Bogen, der er opbygget som politisk, social og racemæssig historie...

  11. Dual enzymatic dynamic kinetic resolution by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase and Candida antarctica lipase B

    KAUST Repository

    Karume, Ibrahim

    2016-10-04

    The immobilization of Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (TeSADH) using sol–gel method enables its use to racemize enantiopure alcohols in organic media. Here, we report the racemization of enantiopure phenyl-ring-containing secondary alcohols using xerogel-immobilized W110A TeSADH in hexane rather than the aqueous medium required by the enzyme. We further showed that this racemization approach in organic solvent was compatible with Candida antarctica lipase B (CALB)-catalyzed kinetic resolution. This compatibility, therefore, allowed a dual enzymatic dynamic kinetic resolution of racemic alcohols using CALB-catalyzed kinetic resolution and W110A TeSADH-catalyzed racemization of phenyl-ring-containing alcohols.

  12. Molecular modeling study of chiral drug crystals: lattice energy calculations.

    Science.gov (United States)

    Li, Z J; Ojala, W H; Grant, D J

    2001-10-01

    The lattice energies of a number of chiral drugs with known crystal structures were calculated using Dreiding II force field. The lattice energies, including van der Waals, Coulombic, and hydrogen-bonding energies, of homochiral and racemic crystals of some ephedrine derivatives and of several other chiral drugs, are compared. The calculated energies are correlated with experimental data to probe the underlying intermolecular forces responsible for the formation of racemic species, racemic conglomerates, or racemic compounds, termed chiral discrimination. Comparison of the calculated energies among ephedrine derivatives reveals that a greater Coulombic energy corresponds to a higher melting temperature, while a greater van der Waals energy corresponds to a larger enthalpy of fusion. For seven pairs of homochiral and racemic compounds, correlation of the differences between the two forms in the calculated energies and experimental enthalpy of fusion suggests that the van der Waals interactions play a key role in the chiral discrimination in the crystalline state. For salts of the chiral drugs, the counter ions diminish chiral discrimination by increasing the Coulombic interactions. This result may explain why salt forms favor the formation of racemic conglomerates, thereby facilitating the resolution of racemates.

  13. Concentration-dependent enantioselective transport of chiral timolol maleate across hairless mice skin upon using various concentrations of chiral terpene enhancer (D-Limonene.

    Directory of Open Access Journals (Sweden)

    Mohsen I. Afouna

    2013-12-01

    Full Text Available The objective of the present study was to examine the relationship between different concentrations of the chiral enhancer D- Limonene (D-LM on the solubility of individual enantiomers and racemate Timolol maleate (TM The preferential improvement of D-LM on S-TM, R-TM, and racemate transported across the hairless mice skin was also investigated. For solubility studies, excess of R-, S-, or racemate with different concentrations of D-LM were prepared. The samples were agitated, centrifuged, filtered and analyzed using HPLC with a chiral column at a wavelength of 294 nm. For skin transport studies, formulations containing 0.5% solutions of S-TM, R-TM, or racemate in a buffer solution with predetermined concentrations of D-LM were studied. Samples of 1 ml were withdrawn and quantitatively analyzed for their TM contents. Steady-state fluxes (Jss, permeability coefficients and the enhancement factor were calculated. The studies showed that D-LM significantly increased the solubility of the enantiomeric, as well as, the racemate forms of TM in a concentration dependent manner. The permeation studies showed that the presence of D-LM significantly increased the flux values of both enantiomers and racemate. However, D-LM preferentially increased the permeability characteristics of the S-isomer compared to those of the R-isomer. Solubilities of the enantiomeric and the racemate forms of TM were found to be a single-valued function of D-LM concentration. Moreover, the addition of D-LM increased the transport of the S-TM, R-TM enantiomers and the racemate across the hairless mice skin. In conclusion, all the tested formulations, the overall permeability characteristics of the therapeutically active TM (i.e., S-TM proved to be superior to those obtained with the R-TM either as enantiomer or racemate

  14. Chiral Recognition for the Two Enantiomers of Phenylalanine and Four Amino Acid Derivatives with (S)-Phenylethylamine Derived Nickel(II) Macrocyclic Complex

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jeong Jae; Ryoo, Jae Jeong [Kyungpook National Univ., Daegu (Korea, Republic of)

    2013-11-15

    The potency of new chiral selector candidate was assessed by this simple chiral discrimination test. This experiment showed that the macrocyclic molecule can be a powerful candidate as a chiral selector to obtain optically pure amino acid or amino acid derivatives, particularly phenylalanine and N-benzoyl-phenylalanine enantiomers from racemic mixtures. This study attempted to use the chiral metal organic framework (MOF), 1, as a good chiral selector candidate for the chiral discrimination of racemic phenylalanine, N-benzoyl-alanine, N-benzoyl-phenylalanine, N-benzoyl-methionine, N-CBZ-alanine. The chiral recognition ability of the chiral macromolecule, was examined by varying the molar ratio of the macromolecule and racemates.

  15. Resolution of the Chiral Drugs

    Institute of Scientific and Technical Information of China (English)

    DENG JinGen; ZHU Jin

    2001-01-01

    @@ Chiral drugs are generally not permitted to be used in racemic form so that unintended side effects and unnecessary environmental hazards are avoided. Moreover, homochiral molecules are required immediately to progress key toxicological and clinical studies in the drug discovery. One series of technologies which can rapidly supply homochiral compounds is the separation of racemates, and of those the technique of crystallization of diastereomers is extremely effective-principally because it is simple to operate and it affords both enantiomers. In classical resolution via diastereoisomeric salt formation, the resolved compounds are limited to a given racemic acid or base and the choice of a suitable resolving agent for a racemic target compound is achieved by time-consuming trial-and-error procedure.

  16. Interim Policy for Evaluation of Stereoisomeric Pesticides

    Science.gov (United States)

    An interim approach for determining data requirements for non-racemic mixtures of stereoisomeric pesticides. These data are needed in order to assess the risk posed to ecosystems and drinking water sources by these mixtures.

  17. Enantioselective esterification of (R,S)-2-methylalkanoic acid with Carica papaya lipase in organic solvents.

    Science.gov (United States)

    Chang, Chun-Sheng; Ho, Ssu-Ching

    2011-11-01

    Isooctane was the best reaction medium for the enantioselective esterification of (R,S)-2-methylalkanoic acid with n-butanol using Carica papaya lipase as catalyst. Increasing linear alkyl-chain length of racemic 2-methylalkanoic acids from ethyl to hexyl increased the enantioselectivity (E) from 2.1 to 98.2 for the esterification of racemic 2-methylalkanoic acids with n-butanol at 35°C. Decreasing reaction temperature from 40 to 20°C increased the enantioselectivity (E) from 14 to 33 for the esterification of racemic 2-methylhexanoic acids with n-butanol. We obtained a maximum enantioselectivity, of E = 24.3, for the enantioselective esterification of racemic 2-methylhexanoic acids with n-butanol in isooctane at water activity 0.33, and at 35°C.

  18. Preliminary studies for the separation of profens by chiral liquid chromatography

    OpenAIRE

    Ribeiro, António E.; Pais, L.S.; Rodrigues, A.E.

    2004-01-01

    The increasing pressure by regulatory authorities against the marketing of racemic mixtures, resulting from considerations of clinical efficacy and consumer safety, led to current efforts in the development of sensitive and efficient techniques

  19. Miniaturized Lab-on-a-Chip Polarimeter Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Life on Earth is unique in many ways; one of its great mysteries is that all the biomolecules of Earth's life are chiral and non-racemic. In our pursuit of life on...

  20. Enantioselective Toxicity and Biotransformation of Fipronil in the Fathead Minnow (Pimephales promelas)

    Science.gov (United States)

    Fipronil is a relatively new chiral phenylpyrazole insecticide used to control both agricultural and household invertebrate pests. Fipronil is applied as a racemate, or equal mixture, of its two enantiomers. As regulations on older pesticides increase, production and applicatio...

  1. Synthesis and antitumor activity of novel 10-amino acids ester homocamptothecin analogues

    Institute of Scientific and Technical Information of China (English)

    Liang You; Wan Nian Zhang; Zhen Yuan Miao; Wei Guo; Xiao Ying Che; Wen Ya Wang; Chun Quan Sheng; Jiang Zhong Yao; Ting Zhou

    2008-01-01

    Nine racemic homocamptothecin derivatives were synthesized and in vitro antitumor activities were evaluated by standard MTT method.The results showed that some of the compound had higher antitumor activity than iritecan.

  2. A consideration of the patentability of enantiomers in the pharmaceutical industry in the United States.

    Science.gov (United States)

    Miller, Chris P; Ullrich, John W

    2008-06-01

    During the last thirty years, concern over stereoselectivity of drug action has drawn a great deal of interest within the pharmaceutical field due to an improved understanding of the pharmacology and pharmacokinetics of enantiomers. Developing single enantiomers versus racemates or introducing a single enantiomer following the development of the racemic mixture appears to be the new trend. The intellectual property status of single enantiomers from racemates may be unclear. Drug discoverers and patent attorneys must examine the examples of the past to establish an appropriate pathway towards the development and intellectual property protection of chiral drugs. The review will focus on the patenting of an enantiomer in view of the prior art disclosure for the racemic mixture.

  3. Stereoselective Actions of Methylenedioxypyrovalerone (MDPV) To Inhibit Dopamine and Norepinephrine Transporters and Facilitate Intracranial Self-Stimulation in Rats

    National Research Council Canada - National Science Library

    Kolanos, R; Partilla, J S; Baumann, M H; Hutsell, B A; Banks, M L; Negus, S S; Glennon, R A

    2015-01-01

    ...) and norepinephrine (NET) that produces a constellation of abuse-related behavioral effects. MDPV possesses a chiral center, and the abused formulation of the drug is a racemic mixture, but no data are available on the pharmacology of its isomers...

  4. A simple explanation of the enhancement or depletion of the enantiomeric excess in the partial sublimation of enantiomerically enriched amino acids.

    Science.gov (United States)

    Bellec, Aurélien; Guillemin, Jean-Claude

    2010-03-07

    In the partial sublimation of three enantiomerically enriched amino acids, the ee of the sublimates can be explained by the ratio between the saturated vapor pressures of the racemate and the pure enantiomers.

  5. Synthesis of Metal-Organic Zeolites with Homochirality and High Porosity for Enantioselective Separation.

    Science.gov (United States)

    Xu, Zhong-Xuan; Liu, Liyang; Zhang, Jian

    2016-07-01

    Using lactic acid derivatives as chiral ligands, a pair of unprecedented homochiral metal-organic zeolites have been synthesized that feature zeotype CAN topology and have high porosity for enantioselective separation of racemates.

  6. Extensive substrate profiling of cyclopentadecanone monooxygenase as Baeyer-Villiger biocatalyst reveals novel regiodivergent oxidations

    NARCIS (Netherlands)

    Fink, Michael J.; Fischer, Thomas C.; Rudroff, Florian; Dudek, Hanna; Fraaije, Marco W.; Mihovilovic, Marko D.

    2011-01-01

    Cyclopentadecanone monooxygenase (CPDMO) is one of the latest additions to the established library of Baeyer-Villiger monooxygenases. Desymmetrizations of substituted cyclobutanones and -hexanones as well as kinetic resolutions of racemic cycloketones are efficiently catalyzed by CPDMO. Moreover the

  7. Integration of reactive membrane extraction with lipase-hydrolysis dynamic kinetic resolution of naproxen 2,2,2-trifluoroethyl thioester in isooctane.

    Science.gov (United States)

    Lu, Chu-Hsun; Cheng, Yu-Chi; Tsai, Shau-Wei

    2002-07-20

    Lipases immobilized on polypropylene powders have been used as the biocatalyst in the enantioselective hydrolysis of (S)-naproxen from racemic naproxen thioesters in isooctane, in which trioctylamine was added to perform in situ racemization of the remaining (R)-thioester substrate. A detailed study of the kinetics for hydrolysis and racemization indicates that increasing the trioctylamine concentration can activate and stabilize the lipase as well as enhance the racemization and non-stereoselective hydrolysis of the thioester. Effects of the aqueous pH value and trioctylamine concentration on (S)-naproxen dissociation and partitioning in the aqueous phase as well as the transportation in a hollow fiber membrane were further investigated. Good agreements between the experimental data and theoretical results were obtained when the dynamic kinetic resolution process was integrated with a hollow fiber membrane to reactively extract the desired (S)-naproxen out of the reaction medium.

  8. Application of the Beauveria bassiana Strain for the Enantioselective Oxidation of the Diethyl 1-Hydroxy-1-Phenylmethanephosphonate

    OpenAIRE

    2010-01-01

    Biotransformation of diethyl 1-hydroxy-1-phenylmethanephosphonate using fungi Beauveria bassiana allowed resolving the racemic mixture of the substrate and due to the biocatalyst and reaction conditions modifications, leading to desired optical isomer.

  9. Resolution of the Chiral Drugs

    Institute of Scientific and Technical Information of China (English)

    DENG; JinGen

    2001-01-01

    Chiral drugs are generally not permitted to be used in racemic form so that unintended side effects and unnecessary environmental hazards are avoided. Moreover, homochiral molecules are required immediately to progress key toxicological and clinical studies in the drug discovery. One series of technologies which can rapidly supply homochiral compounds is the separation of racemates, and of those the technique of crystallization of diastereomers is extremely effective-principally because it is simple to operate and it affords both enantiomers. In classical resolution via diastereoisomeric salt formation, the resolved compounds are limited to a given racemic acid or base and the choice of a suitable resolving agent for a racemic target compound is achieved by time-consuming trial-and-error procedure.  ……

  10. Mimosaceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1973-01-01

    Herbs, shrubs or trees, sometimes climbers. Leaves alternate, bipinnate or rarely pinnate. Stipules present, often modified as spines. Inflorescence capitate, spicate, umbellate or racemose, solitary or arranged in racemes, panicles or fascicles. Flowers actinomorphic, 4- or 5-merous, hermaphrodite

  11. Pentaphylacaceae

    NARCIS (Netherlands)

    Steenis, van C.G.G.J.

    1955-01-01

    Evergreen, subglabrous shrubs or trees. Twigs lengthwise grooved and ridged. Buds perular. Leaves simple, entire, penninerved, spirally arranged; midrib and petiole sulcate. Stipules absent. Flowers bisexual, actinomorphic, rather small, in ± sessile, bracteate, axillary pseudo-spikes or -racemes wh

  12. Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation

    DEFF Research Database (Denmark)

    Fristrup, Peter; Lassen, Peter Rygaard; Tanner, David Ackland;

    2008-01-01

    The three possible dimethylsubstituted phenyloxiranes (cis, trans and geminal) were synthesized in both racemic (mCPBA) and enantiomerically enriched forms (Shi epoxidation) and subjected to a vibrational circular dichroism study. The experimental spectra were compared to theoretical spectra obta...

  13. Crystalline architectures at the air-liquid interface: From nucleation to engineering

    DEFF Research Database (Denmark)

    Rapaport, H.; Kuzmenko, I.; Kjær, K.

    1999-01-01

    here shall encompass the spontaneous separation of racemates of amphiphilic molecules into enantiomorphous two-dimensional (2D) domains, the formation of alkane multilayers, the assembly of trilayers containing interdigitated molecules, the self-organization of supramolecular thin film architectures...

  14. Inhibitory effects of gossypol, gossypolone, and apogossypolone on a collection of economically important filamentous fungi

    Science.gov (United States)

    Racemic gossypol and derivatives gossypolone and apogossypolone demonstrated significant growth inhibition against a diverse collection of filamentous fungi that included Aspergillus flavus, A. parasiticus, A. alliaceus, A. fumigatus, Fusarium graminearum, F. moniliforme, Penicillium chrysogenum, P....

  15. 3-methylaminopropylamine as a templating agent in the synthesis of phosphate-based inorganic polymers

    Directory of Open Access Journals (Sweden)

    Jevtić Sanja O.

    2013-01-01

    Full Text Available 3-methylaminopropylamine (MPA has been studied as a structure-directing agent (template in the synthesis of open-framework phosphate-based materials. The influence of temperature, molar ratio of reactants, crystallization time and presence of fluoride ions on the crystallization of aluminophosphate, transition metal-substituted aluminophosphate [transition metal - Mn(II, Cr(III and Co(II] and zincophosphate has also been investigated. MPA exhibits the templating role and in all as-synthesized crystalline products and it is entrapped in an inorganic lattice interacting with the framework via hydrogen or/and electrostatic interactions. According to detailed thermal analysis the type of interactions seems to be crucial for thermal behaviour of MPA and also for the thermal stability of the organic-inorganic crystal system. Structural analysis suggested that the formed crystalline structures have no mutual structural analogy. This indicates that precise role of the organic (guest component in nucleation process for the open-framework phosphates (host is very complex as well as the nucleation process itself. [Projekat Ministarstva nauke Republike Srbije, br. 172018

  16. FTIR study of carbon monoxide adsorption on ion-exchanged X, Y and mordenite type zeolites

    Directory of Open Access Journals (Sweden)

    R. HERCIGONJA

    2003-05-01

    Full Text Available In this work Fourier transform infrared (FTIR study has been applied to study the adsorption of carbon monoxide on transition metal (Mn+, Co2+, Ni2+ ion-exchanged zeolites type Y, X and mordenites. The adsorption of CO at room temperature produces overlapping IR absorption bands in the 2120–2200 cm-1 region. The frequency of the band around 2200 cm-1 is found to be dependent not only on the charge-balancing transition metal cation, but also on the framework composition. The frequencies of the band near 1600 cm-1 was found to be dependent on the Si/Al ratio of the investigated zeolites.

  17. Nitrato de amônio ocluído em zeólita 4A: lixiviação e absorção de nitrogênio no cultivo de milho

    Directory of Open Access Journals (Sweden)

    Jardel Cavalcante Rolim de Almeida Andrade

    2011-09-01

    Full Text Available Systematic studies were undertaken in the intra zeolitic media to better understand the ability of zeolite type LTA in occluded nitrogen used in fertilizer and soil conditioning. We have measured the dry matter production from the cultivation of corn in a greenhouse for about 40 days, and also the amounts of nitrogen absorbed, retained and lost by leaching. The dry matter production in the cultivation with different concentrations of nitrogen occluded in the zeolite, was more efficient than the traditional fertilizer, which demonstrated better use of nitrogen to reduce leaching losses, which implies a possible reduction of costs for nitrogen.

  18. Synthesis and applications of novel bis(ammonium) chiral ionic liquids derived from isomannide

    DEFF Research Database (Denmark)

    Kumar, Vineet; Olsen, Carl Erik; Schäffer, Susan J.;

    2007-01-01

    Carbohydrate-based novel bis(ammonium) chiral ionic liquids have been synthesized by following a straightforward protocol using isomannide as the substrate. Their applications in chiral discrimination and optical resolution of racemates have been established.......Carbohydrate-based novel bis(ammonium) chiral ionic liquids have been synthesized by following a straightforward protocol using isomannide as the substrate. Their applications in chiral discrimination and optical resolution of racemates have been established....

  19. Resolution of 2,3-dihydro-benzofuran-3-ols

    Indian Academy of Sciences (India)

    Cédric Charrier; Philippe Bertrand

    2011-07-01

    A new method for the preparation of enantiopure 2,2-disubstituted 2,3-dihydro-benzofuran-3-ols is described. A short synthesis is designed for obtaining various 2,2-disubstitued benzofuran-3-ols as racemic mixtures of the two possible syn and anti diastereoisomers, which can be separated after silylation. The major racemic anti isomers were transesterified using (R)-pentolactone, allowing separation of the pure enantiomers.

  20. Synthesis of Bis-pyrrolizidine-Fused Dispiro-oxindole Analogues of Curcumin via One-Pot Azomethine Ylide Cycloaddition: Experimental and Computational Approach toward Regio- and Diastereoselection.

    Science.gov (United States)

    Bharitkar, Yogesh P; Das, Mohua; Kumari, Neha; Kumari, M Padma; Hazra, Abhijit; Bhayye, Sagar S; Natarajan, Ramalingam; Shah, Siddharth; Chatterjee, Sourav; Mondal, Nirup B

    2015-09-18

    Curcumin has been transformed to racemic curcuminoids via an azomethine ylide cycloaddition reaction using isatin/acenaphthoquinone and proline as the reagents. The products were characterized by extensive 1D/2D NMR analysis and single-crystal X-ray crystallographic studies. The enantiomers of one racemic product were separated by HPLC on a Chiralcel OD-H column and were indeed confirmed by the CD spectra of the separated enantiomers.

  1. Absolute configuration and crystal packing for three chiral drugs prone to spontaneous resolution: Guaifenesin, methocarbamol and mephenesin

    Science.gov (United States)

    Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.; Krivolapov, Dmitry B.; Pashagin, Alexander V.; Litvinov, Igor A.

    2009-02-01

    Popular chiral drugs, guaifenesin, methocarbamol, and mephenesin were investigated by single-crystal X-ray analysis both for enantiopure and racemic samples. The absolute configurations for all substances were established through Flack parameter method. The conglomerate-forming nature for the compounds was confirmed by equivalence of crystal characteristics of enantiopure and racemic samples. The molecular structures and crystal packing details were evaluated and compared with one another for all three investigated substances.

  2. One hydrogen bond does not a separation make, or does it?

    DEFF Research Database (Denmark)

    Báthori, Nikoletta B; Nassimbeni, Luigi R; van de Streek, Jacco

    2015-01-01

    Diacetoneketogulonic acid was used to separate primary amines from their racemic modifications and the selectivity of the acid was rationalized by lattice energy calculations and analyzing the weak interactions around the captured amines.......Diacetoneketogulonic acid was used to separate primary amines from their racemic modifications and the selectivity of the acid was rationalized by lattice energy calculations and analyzing the weak interactions around the captured amines....

  3. Separation of enantiomers

    CERN Document Server

    Todd , Matthew H

    2014-01-01

    In one handy volume this handbook summarizes the most common synthetic methods for the separation of racemic mixtures, allowing an easy comparison of the different strategies described in the literature.Alongside classical methods, the authors also consider kinetic resolutions, dynamic kinetic resolutions, divergent reactions of a racemic mixture, and a number of ""neglected"" cases not covered elsewhere, such as the use of circularly polarized light, polymerizations, ""ripening"" processes, dynamic combinatorial chemistry, and several thermodynamic processes. The result is a thorough introdu

  4. Enantiospecific ketoprofen concentrations in plasma after oral and intramuscular administration in growing pigs

    OpenAIRE

    Mustonen Katja; Niemi Anneli; Raekallio Marja; Heinonen Mari; Peltoniemi Olli AT; Palviainen Mari; Siven Mia; Peltoniemi Marikki; Vainio Outi

    2012-01-01

    Abstract Background Ketoprofen is a non-steroidal anti-inflammatory drug which has been widely used for domestic animals. Orally administered racemic ketoprofen has been reported to be absorbed well in pigs, and bioavailability was almost complete. The objectives of this study were to analyze R- and S-ketoprofen concentrations in plasma after oral (PO) and intra muscular (IM) routes of administration, and to assess the relative bioavailability of racemic ketoprofen for both enantiomers betwee...

  5. L—PROLINE—FUNCTIONALIZED POLYSTYRENE WITH 1—METHYLDECYLENE SPACER AS A CHIRAL STATIONARY PHASE FOR LIGAND—EXCHANGE CHROMATOGRAPHIC RESOLUTION OF AMINO ACID RECEMATES

    Institute of Scientific and Technical Information of China (English)

    MaJianbiao; ChenLi; 等

    1995-01-01

    The L-proline-functionalized polystyrene with 1-methyldecylene spacer was synthesized from 2% divinylbenzene-crosslinked polystyrene gel via 10-bromo-1-methyldecyl polystyrene intermediate.After complexed with copper(Ⅱ) ion,the polymer with L-proline ligand was used as the chiral stationary phase (CSP) for ligand exchange chromatography of amino acid racemates.The results showed that the CSP possessed powerful enantioselectivity and all racemates of the fifteen tried amino acids were completely separated.

  6. Den radikale Kings skandinaviske drøm

    DEFF Research Database (Denmark)

    Brøndal, Jørn

    2013-01-01

    I dag forgudes Martin Luther King for sin racemæssige vision. Derimod aner de fleste amerikanere ikke noget om hans økonomiske ideer, og hvis de gjorde, ville mange af dem utvivlsomt affeje dem som alt for radikale......I dag forgudes Martin Luther King for sin racemæssige vision. Derimod aner de fleste amerikanere ikke noget om hans økonomiske ideer, og hvis de gjorde, ville mange af dem utvivlsomt affeje dem som alt for radikale...

  7. Chromatographic Enantioseparations in Achiral Environments: Myth or Truth?

    Science.gov (United States)

    Martens, Jürgen; Bhushan, Ravi; Sajewicz, Mieczyslaw; Kowalska, Teresa

    2017-08-01

    Direct chromatographic enantioseparations are among the most important practical tasks of chromatography. The accepted rules and concepts of stereochemistry anticipated one type of chromatographic systems applicable only to such enantioseparations consisting either of chiral stationary phase, or chiral selector present in mobile phase. In such a model of chromatographic system, both racemic and non-racemic mixtures could be enantioseparated. Over the years, however, reports on successful chiral enantioseparations in non-chiral chromatographic systems have cumulated as well. To adapt the initial model to novel experimental evidence, an assumption had to be added stating that these were only non-racemic mixtures (and not racemic ones), which could be enantioseparated in achiral chromatographic systems, by granting them an inevitable chirality from the enantiomeric excess of a more abundant enantiomer. There still exists an overlooked portion of experimental evidence for successful enantioseparations of racemic mixtures in the non-chiral chromatographic systems, which cannot be explained by the accepted model. Facing this incompatibility between the model and practical results, we reflect on how to reconcile these two by questioning the possibility of pinpointing a true racemate with the help of our imperfect analytical tools. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  8. Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms.

    Science.gov (United States)

    Demirci, Selami; Ustaoğlu, Zeynep; Yılmazer, Gonca Altın; Sahin, Fikrettin; Baç, Nurcan

    2014-02-01

    Zeolites are nanoporous alumina silicates composed of silicon, aluminum, and oxygen in a framework with cations, water within pores. Their cation contents can be exchanged with monovalent or divalent ions. In the present study, the antimicrobial (antibacterial, anticandidal, and antifungal) properties of zeolite type X and A, with different Al/Si ratio, ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions were investigated individually. The study presents the synthesis and manufacture of four different zeolite types characterized by scanning electron microscopy and X-ray diffraction. The ion loading capacity of the zeolites was examined and compared with the antimicrobial characteristics against a broad range of microorganisms including bacteria, yeast, and mold. It was observed that Ag(+) ion-loaded zeolites exhibited more antibacterial activity with respect to other metal ion-embedded zeolite samples. The results clearly support that various synthetic zeolites can be ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions to acquire antimicrobial properties or ion-releasing characteristics to provide prolonged or stronger activity. The current study suggested that zeolite formulations could be combined with various materials used in manufacturing medical devices, surfaces, textiles, or household items where antimicrobial properties are required.

  9. Responses by Dendroctonus frontalis and Dendroctonus mesoamericanus (Coleoptera: Curculionidae) to Semiochemical Lures in Chiapas, Mexico: Possible Roles of Pheromones During Joint Host Attacks.

    Science.gov (United States)

    Niño-Domínguez, Alicia; Sullivan, Brian T; López-Urbina, José H; Macías-Sámano, Jorge E

    2016-04-01

    In southern Mexico and Central America, the southern pine beetle Dendroctonus frontalis Zimmermann (Coleoptera: Curculionidae: Scolytinae) commonly colonizes host trees simultaneously with Dendroctonus mesoamericanus Armendáriz-Toledano and Sullivan, a recently described sibling species. We hypothesized that cross-species pheromone responses by host-seeking beetles might mediate joint mass attack, bole partitioning, and reproductive isolation between the species. Previous studies had indicated that D. frontalis females produce frontalin and that female D. mesoamericanus produce frontalin, endo-brevicomin, and ipsdienol (males of both species produce endo-brevicomin and possibly ipsdienol). In field trapping trials in the Mexican state of Chiapas, D. frontalis was attracted to the lure combination of turpentine and racemic frontalin; racemic endo-brevicomin enhanced this response. In a single test, D. mesoamericanus was attracted in low numbers to the combination of turpentine, racemic frontalin, and racemic endo-brevicomin after the addition of racemic ipsdienol; in contrast, racemic ipsdienol reduced responses of D. frontalis. Inhibition of D. frontalis was generated in both sexes by (+)- and racemic ipsdienol, but by (−)-ipsdienol only in females. Logs infested with D. mesoamericanus females (the pioneer sex in Dendroctonus) attracted both species in greater numbers than either D. frontalis female-infested or uninfested logs. Our data imply that D. frontalis may be more attracted to pioneer attacks of D. mesoamericanus females, and that this could be owing to the presence of endo-brevicomin in the latter. Possible intra- and inter-specific functions of semiochemicals investigated in our experiments are discussed.

  10. Field responses of the Asian larch bark beetle, Ips subelongatus, to potential aggregation pheromone components: disparity between two populations in northeastern China

    Institute of Scientific and Technical Information of China (English)

    Li-Wen Song; Qing-He Zhang; Yue-Qu Chen; Tong-Tong Zuo; Bing-Zhong Ren

    2011-01-01

    Behavioral responses of the Asian larch bark beetle, Ips subelongatus Motsch. to three potential aggregation pheromone components, ipsenol (racemic or [-]-enantiomer), ipsdienol (racemic or [+]-enantiomer) and 3-methyl-3-buten-1 -ol, were tested using partial or full factorial experimental designs in two provinces (Inner Mongolia and Jilin) of northeastern China. Our field bioassays in Inner Mongolia (Larix principis- rupprechtii Mayr. plantation) clearly showed that ipsenol, either racemic or 97%-(-)-enantiomer, was the only compound that significantly attracted both sexes of I. subelongatus, while all other compounds (singly or in combinations) were unattractive. There were no two- or three-way synergistic interactions. However, in Jilin Province (L. gmelini [Rupr.] Rupr. Plantation), all the individual compounds tested were inactive, except a very weak activity by 97%-(-)-ipsenol in 2004 when the beetle population was very high. While a combination of ipsenol and ipsdienol (racemates or enantiomerically pure natural enantiomers) showed a significant attraction for both sexes of I. subelongatus, indicating a two-way synergistic interaction between these two major components, addition of 3-methyl-3-buten-l-ol to these active binary blend(s) did not have any effects on trap catches, suggesting that ipsenol and ipsdienol are the synergistic aggregation pheromone components of I. subelongatus in Jilin Province. It seems that 97%-(-)-ipsenol in Inner Mongolia or the binary blend of 97%-(-)-ipsenol and 97%-(+)-ipsdienol in Jilin Province are superior to their corresponding racemates, which might be due either to weak inhibitory effects of the antipode enantiomers or to reduced release rates of the active natural enantiomers) in the racemate(s). Our current bioassay results suggest that there is a strong geographical variation in aggregation pheromone response of I. subelongatus in northeastern China. Future research on the pheromone production and response of I

  11. Stereoselective Effects of Abused “Bath Salt” Constituent 3,4-Methylenedioxypyrovalerone in Mice: Drug Discrimination, Locomotor Activity, and Thermoregulation

    Science.gov (United States)

    Gannon, Brenda M.; Williamson, Adrian; Suzuki, Masaki; Rice, Kenner C.

    2016-01-01

    3,4-Methylenedioxypyrovalerone (MDPV) is a common constituent of illicit “bath salts” products. MDPV is a chiral molecule, but the contribution of each enantiomer to in vivo effects in mice has not been determined. To address this, mice were trained to discriminate 10 mg/kg cocaine from saline, and substitutions with racemic MDPV, S(+)-MDPV, and R(−)-MDPV were performed. Other mice were implanted with telemetry probes to monitor core temperature and locomotor responses elicited by racemic MDPV, S(+)-MDPV, and R(−)-MDPV under a warm (28°C) or cool (20°C) ambient temperature. Mice reliably discriminated the cocaine training dose from saline, and each form of MDPV fully substituted for cocaine, although marked potency differences were observed such that S(+)-MDPV was most potent, racemic MDPV was less potent than the S(+) enantiomer, and R(−)-MDPV was least potent. At both ambient temperatures, locomotor stimulant effects were observed after doses of S(+)-MDPV and racemic MDPV, but R(−)-MDPV did not elicit locomotor stimulant effects at any tested dose. Interestingly, significant increases in maximum core body temperature were only observed after administration of racemic MDPV in the warm ambient environment; neither MDPV enantiomer altered core temperature at any dose tested, at either ambient temperature. These studies suggest that all three forms of MDPV induce biologic effects, but R(−)-MDPV is less potent than S(+)-MDPV and racemic MDPV. Taken together, these data suggest that the S(+)-MDPV enantiomer is likely responsible for the majority of the biologic effects of the racemate and should be targeted in therapeutic efforts against MDPV overdose and abuse. PMID:26769917

  12. Stereoselective Effects of Abused "Bath Salt" Constituent 3,4-Methylenedioxypyrovalerone in Mice: Drug Discrimination, Locomotor Activity, and Thermoregulation.

    Science.gov (United States)

    Gannon, Brenda M; Williamson, Adrian; Suzuki, Masaki; Rice, Kenner C; Fantegrossi, William E

    2016-03-01

    3,4-Methylenedioxypyrovalerone (MDPV) is a common constituent of illicit "bath salts" products. MDPV is a chiral molecule, but the contribution of each enantiomer to in vivo effects in mice has not been determined. To address this, mice were trained to discriminate 10 mg/kg cocaine from saline, and substitutions with racemic MDPV, S(+)-MDPV, and R(-)-MDPV were performed. Other mice were implanted with telemetry probes to monitor core temperature and locomotor responses elicited by racemic MDPV, S(+)-MDPV, and R(-)-MDPV under a warm (28°C) or cool (20°C) ambient temperature. Mice reliably discriminated the cocaine training dose from saline, and each form of MDPV fully substituted for cocaine, although marked potency differences were observed such that S(+)-MDPV was most potent, racemic MDPV was less potent than the S(+) enantiomer, and R(-)-MDPV was least potent. At both ambient temperatures, locomotor stimulant effects were observed after doses of S(+)-MDPV and racemic MDPV, but R(-)-MDPV did not elicit locomotor stimulant effects at any tested dose. Interestingly, significant increases in maximum core body temperature were only observed after administration of racemic MDPV in the warm ambient environment; neither MDPV enantiomer altered core temperature at any dose tested, at either ambient temperature. These studies suggest that all three forms of MDPV induce biologic effects, but R(-)-MDPV is less potent than S(+)-MDPV and racemic MDPV. Taken together, these data suggest that the S(+)-MDPV enantiomer is likely responsible for the majority of the biologic effects of the racemate and should be targeted in therapeutic efforts against MDPV overdose and abuse. U.S. Government work not protected by U.S. copyright.

  13. Toxicokinetic assessment of methylphenidate (Ritalin) enantiomers in pregnant rats and rabbits.

    Science.gov (United States)

    Bakhtiar, Ray; Tse, Francis L S

    2004-06-01

    Ritalin or methylphenidate (MPH) is prescribed for the treatment of attention deficit hyperactivity disorder (ADHD) and narcolepsy. The present report describes the determination of plasma concentrations of D-threo- and L-threo-enantiomers of MPH in toxicokinetic (TK) studies in pregnant Wistar Hannover rats and New Zealand white rabbits following repeated daily oral dosing of D,L-MPH (racemate). A previously reported chiral liquid chromatography tandem mass spectrometric (LC-MS/MS) method with a lower limit of quantification (LLOQ) of 1.09 ng/mL was utilized. Oral (gavage) doses of 7, 25 and 75 mg/kg/day of racemic MPH were selected for the rat study. An over-proportional increase in exposure was observed with increasing doses of MPH racemate, the effect being more profound with the D- than the L-enantiomer. In contrast, Cmax values of both enantiomers were approximately proportional to the dose. Oral (gavage) doses of 20, 60 and 200 mg/kg were selected for the rabbit study. In general, for the D-isomer, an over-proportional increase in exposure was observed with increasing doses of MPH racemate. Conversely, for the L-isomer, a slight under-proportionality was detected in exposure with increasing doses of D,L-MPH. For mean Cmax, while L-isomer exhibited dose proportionality with increasing doses of MPH racemate, the D-isomer appeared to be over-proportional. Herein, the experimental design and observed TK parameters in each study are presented.

  14. Stereoselective pharmacokinetics of stiripentol: an explanation for the development of tolerance to anticonvulsant effect.

    Science.gov (United States)

    Arends, R H; Zhang, K; Levy, R H; Baillie, T A; Shen, D D

    1994-06-01

    An earlier pharmacodynamic study of the chiral antiepileptic drug stiripentol in an intravenous pentylenetetrazol-induced seizure model in the rat showed the development of a significant degree of tolerance to the anticonvulsant and neurotoxic effects following subacute treatment with the racemic compound. A more recent study with the pure enantiomers of stiripentol indicated that the (+)-enantiomer is 2.4 times more potent than the (-)-enantiomer, based on a comparison of brain EC50 values for the anticonvulsant effect. Moreover, (-)-stiripentol has a much longer elimination half-life than (+)-stiripentol. We have re-analyzed the brain and blood samples from the first pharmacodynamic study using a newly developed chiral HPLC assay to investigate whether the tolerance phenomenon with racemic stiripentol was due to a shift in the enantiomeric composition of stiripentol in brain tissue during repetitive administration of racemic drug. A large increase, as much as 5-6-fold, in the (-)/(+) ratio in brain concentration of stiripentol was observed after subacute administration, as compared with that after a single dose of the racemic drug. The enrichment in the less potent enantiomers during repetitive drug administration explains the previous observation of an apparent development of tolerance when the pharmacologic effects were related to total [(-)+(+)] brain concentrations of stiripentol as measured by a non-stereoselective assay. The results of this study highlight the importance of stereoselective pharmacokinetics in investigating the pharmacodynamics of the racemic mixture of a chiral anticonvulsant.

  15. Ketamine for Depression, 3: Does Chirality Matter?

    Science.gov (United States)

    Andrade, Chittaranjan

    2017-06-01

    Ketamine is a racemic mixture of the enantiomers R-ketamine and S-ketamine (esketamine). S-ketamine has greater analgesic and anesthetic effects than R-ketamine and is less likely to cause psychotomimetic and other adverse effects. There is therefore an emerging interest favoring the use of S-ketamine over racemic ketamine when the drug is used for analgesia or anesthesia. This article examines preclinical and clinical literature on the antidepressant properties of S-ketamine. Animal data suggest potential advantages for R-ketamine over S-ketamine. Case reports, case series, and some small randomized controlled trials suggest that single or repeated intravenous infusions (0.2-0.4 mg/kg) or intranasal administrations (28-84 mg) of S-ketamine have antidepressant action in patients with medication-refractory depression and that the observed benefits are similar in magnitude to the antidepressant benefits reported with racemic ketamine. However, there are no direct comparisons between S-ketamine and either R-ketamine or racemic ketamine in depressed patients; therefore, it is not possible to make an informed choice when considering the enantiomers and the racemate for the indication of depression. © Copyright 2017 Physicians Postgraduate Press, Inc.

  16. Transition Metal Titanophosphates with Intercalated Molecular Photoluminescence and Catalytic Properties.

    Science.gov (United States)

    Hung, Ling-I; Chen, Pei-Lin; Yang, Jia-Hao; Peng, Chi-How; Wang, Sue-Lein

    2017-08-10

    In this study, α-TiP layered structure incorporating a heterometal center for organic ligand binding to enhance structural complexity and functionality were prepared. The protons of the α-TiP layer were replaced with zinc ions coordinated by 4-pyridinecarboxylic acid (PCA) and water to form a layer structure, TiZn(PO4 )2 (H2 O)(PCA) (1). The tetrahedral zinc center with coordinated water in 1 is unprecedented in zincophosphate or zinc-MOF systems and is usually only found in metalloenzyme systems. The neutral zincotitanophosphate layers, tightly stacked through hydrogen bonds, showed velcro-like behavior on intercalating 4,4'-trimethylenedipyridine (TMDP) reversibly. It rendered a remarkable luminescence property to 1, emitting blue-to-white light under UV excitation. Surprisingly, the replacement of TMDP for PCA in the hydrothermal synthesis still resulted in 1, plus another structure, Ti4 Zn2 (H2 TPB)(PO4 )4 (HPO4 )4 (H2 PO4 )2 (2) (TPB=1,2,4,5-tetra(4-pyridyl)benzene). Clearly, in situ C-C cracking and C-C coupling of TMDP simultaneously occurred to generate PCA and TPB and thereafter the oxidant, Zn(NO3 )2 , was quantitatively determined to isolate crystal 1 from 2. The structure of 2 also featured α-TiP layers with pedant Zn tetrahedra but formed a three-dimensional neutral framework through TPB. For the first time, α-TiP-derived structures and their properties have been elucidated, which help in understanding intriguing in situ ligand formation and intercalation-induced luminescence, to exploit potential photocatalysis in polymerization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Spontaneous chiral resolution in two-dimensional systems of patchy particles

    Energy Technology Data Exchange (ETDEWEB)

    Martínez-González, J. A.; Chapela, G. A. [Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, 09340 México D.F. (Mexico); Quintana-H, J., E-mail: jaq@unam.mx [Instituto de Química, Universidad Nacional Autónoma de México - Apdo. Postal 70213, 04510 Coyoacán, México D.F. (Mexico)

    2014-05-21

    Short ranged potentials and their anisotropy produce spontaneous chiral resolution in a two dimensional model of patchy particles introduced in this paper. This model could represent an equimolar binary mixture (racemic mixture) of two kinds of chiral molecules (enantiomers) adsorbed to a bi-dimensional domain where only lateral short ranged interactions are present. Most racemic mixtures undergo chiral resolution due to their spatial anisotropy, the combined effect of long range forces and the thermodynamic conditions. The patchy particles are modeled as a hard disk and four different bonding sites located to produce chirality. Phase behavior and structural properties are analysed using Discontinuous Molecular Dynamics in the canonical ensemble. When the four patchy particles are separated by the angles (60°, 120°, 60°, 120°), spontaneous chiral resolution is produced, given by the formation of homochiral clusters, if started from the corresponding racemic mixture. Gel behavior is also obtained in all the systems for low temperatures and low densities.

  18. Detection of the Previously Unobserved Stereoisomers of Thujone in the Essential Oil and Consumable Products of Sage (Salvia officinalis L.) Using Headspace Solid-Phase Microextraction-Gas Chromatography-Mass Spectrometry.

    Science.gov (United States)

    Williams, Jack D; Yazarians, Jessica A; Almeyda, Chelcie C; Anderson, Kristin A; Boyce, Gregory R

    2016-06-01

    The discovery of the (+)-α-thujone and (-)-β-thujone stereoisomers in the essential oil of sage (Salvia officinalis L.) and dietary supplements is documented for the first time. The detection was accomplished using a chiral resolution protocol of racemic α-/β-thujone on headspace solid-phase microextraction-gas chromatography-mass spectrometry. Because the previously unreported stereoisomers, (+)-α-thujone and (-)-β-thujone, are not commercially available, a three-step synthesis of racemic thujone from commercially available starting materials was developed. Thermolysis studies demonstrated that no racemization at the cyclopropane stereocenters occurs, corroborating that the detection is not an artifact from the hydrodistillation process. The developed chiral resolution of thujone was also used to provide evidence for the absence of the (+)-α-thujone and (-)-β-thujone enantiomers in other common thujone-containing essential oils.

  19. Development of safer molecules through chirality

    Directory of Open Access Journals (Sweden)

    Patil P

    2006-10-01

    Full Text Available Many of the drugs currently used in medical practice are mixtures of enantiomers (racemates. Many a times, the two enantiomers differ in their pharmacokinetic and pharmacodynamic properties. Replacing existing racemates with single isomers has resulted in improved safety and/or efficacy profile of various racemates. In this review, pharmacokinetic and pharmacodynamic implications of chirality are discussed in brief, followed by an overview of some important chiral switches that have yielded safer alternatives. These include levosalbutamol, S-ketamine, levobupivacaine, S-zopiclone, levocetirizine, S-amlodipine, S-atenolol, S-metoprolol, S-omeprazole, S-pantoprazole and R-ondansetron. Few potential chiral switches under evaluation and some chiral switches that have not been successful are also discussed.

  20. (±)-Homocrepidine A, a Pair of Anti-inflammatory Enantiomeric Octahydroindolizine Alkaloid Dimers from Dendrobium crepidatum.

    Science.gov (United States)

    Hu, Yang; Zhang, Chaofeng; Zhao, Xin; Wang, Yue; Feng, Deqiang; Zhang, Mian; Xie, Haifeng

    2016-01-22

    A pair of racemic indolizidine enantiomers, (±)-homocrepidine A (1), and a piperidine derivative, homocrepidine B (2), were isolated from Dendrobium crepidatum along with the known alkaloid crepidine (3). The racemic mixture of 1 was separated into a pair of enantiomers, (+)-1 and (-)-1, by HPLC using a chiral chromatographic substrate, which represents the first successful example of resolving indolizidine racemic mixtures. The absolute configurations of (+)-1 and (-)-1 were assigned from single-crystal X-ray diffraction data. The evaluation of anti-inflammatory activity with LPS-induced RAW 264.7 macrophages revealed that (+)-1 strongly inhibited the production of nitric oxide (IC50, 3.6 μM) and significantly decreased the expression of inducible nitric oxide synthase, while (-)-1 and (±)-1 only had moderate inhibitory effects (IC50, 22.8 and 14.7 μM). Compound 2 showed moderate anti-inflammatory activity (IC50, 27.6 μM).

  1. Self-assembly of metallosupramolecular rhombi from chiral concave 9,9’-spirobifluorene-derived bis(pyridine ligands

    Directory of Open Access Journals (Sweden)

    Rainer Hovorka

    2014-02-01

    Full Text Available Two new 9,9’-spirobifluorene-based bis(4-pyridines were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp2M2L2] rhombi with cis-protected [(dpppPd]2+ and [(dpppPt]2+ ions. The self-assembly process of the racemic ligand preferably occurs in a narcissistic self-recognising manner. Hence, a mixture of all three possible stereoisomers [(dppp2M2{(R-L}2](OTf4, [(dppp2M2{(S-L}2](OTf4, and [(dppp2M2{(R-L}{(S-L}](OTf4 was obtained in an approximate 1.5:1.5:1 ratio which corresponds to an amplification of the homochiral assemblies by a factor of approximately three as evidenced by NMR spectroscopy and mass spectrometry. The racemic homochiral assemblies could also be characterised by single crystal X-ray diffraction.

  2. A comparison of the antimalarial activity of the cinchona alkaloids against Plasmodium falciparum in vitro.

    Science.gov (United States)

    Wesche, D L; Black, J

    1990-06-01

    The effects of four major cinchona alkaloids: (-) quinine, (+) quinidine, (-)cinchonidine, and (+)cinchonine against Plasmodium falciparum FCQ-27/PNG were studied. The alkaloids were tested in vitro as either single alkaloids, racemic mixtures of stereoisomers, or as an equimolar combination of all four alkaloids. Results indicate (+)quinidine to be most effective and both (+)stereoisomers were more potent than the (-)stereoisomers. Inhibitory concentrations 50% (Ki) of racemic mixtures of stereoisomers were similar to those of the (+)stereoisomers alone. The Ki of four alkaloids in equimolar combination were similar to that of the (-) cinchonidine/(+)cinchonine racemic mixture. A total alkaloidal extract of Cinchona sp. was tested and compared with the pure alkaloids. HPLC analysis indicated that (+)cinchonine, (-)cinchonidine and (-)quinine were present in a ratio of approximately 1:1:2, respectively. The total alkaloid extract, with (-)stereoisomers predominating, was less effective than the four alkaloids in combination. The nature of the interaction between stereoisomers was investigated and appears to be one of addition.

  3. Polarimetric Detection of Enantioselective Adsorption by Chiral Au Nanoparticles – Effects of Temperature, Wavelength and Size

    Directory of Open Access Journals (Sweden)

    Nisha Shukla

    2015-01-01

    Full Text Available R- and S-propylene oxide (PO have been shown to interact enantiospecifically with the chiral surfaces of Au nanopar‐ ticles (NPs modified with D- or L-cysteine (cys. This enantiospecific interaction has been detected using optical polarimetry measurements made on solutions of the D- or L-cys modified Au (cys/Au NPs during addition of racemic PO. The selective adsorption of one enantiomer of the PO onto the cys/Au NP surfaces results in a net rotation of light during addition of the racemic PO to the solution. In order to optimize the conditions used for making these measurements and to quantify enantiospecific adsorption onto chiral NPs, this work has measured the effect of temperature, wavelength and Au NP size on optical rotation by solutions containing D- or L-cys/Au NPs and racemic PO. Increasing temperature, decreasing wave‐ length and decreasing NP size result in larger optical rotations.

  4. A multi-enzymatic cascade reaction for the stereoselective production of γ-oxyfunctionalyzed amino acids

    Directory of Open Access Journals (Sweden)

    Junichi eEnoki

    2016-04-01

    Full Text Available A stereoselective three-enzyme cascade for synthesis of diasteromerically pure γ-oxyfunctionalized α-amino acids was developed. By coupling a dynamic kinetic resolution using an N-acylamino acid racemase and an L-selective aminoacylase from Geobacillus thermoglucosidasius with a stereoselective isoleucine dioxygenase from Bacillus thuringiensis, diastereomerically pure oxidized amino acids were produced from racemic N-acetylamino acids. The three enzymes differ in their optimal temperature and pH-spectra. Their different metal cofactor dependencies lead to inhibitory effects. Under optimized conditions, racemic N-acetylmethionine was quantitatively converted into L-methionine-(S-sulfoxide with 97% conversion and 95% de. The combination of these three different biocatalysts allows the direct synthesis of diastereopure oxyfunctionalized amino acids from inexpensive racemic starting material.

  5. New 1,4-dihydropyridines endowed with NO-donor and calcium channel agonist properties.

    Science.gov (United States)

    Visentin, Sonja; Rolando, Barbara; Di Stilo, Antonella; Fruttero, Roberta; Novara, Monica; Carbone, Emilio; Roussel, Christian; Vanthuyne, Nicolas; Gasco, Alberto

    2004-05-06

    A new series of calcium channel agonists structurally related to Bay K8644, containing NO donor furoxans and the related furazans unable to release NO, is described. The racemic mixtures were studied for their action on L-type Ca(2+) channels expressed in cultured rat insulinoma RINm5F cells. All the products proved to be potent calcium channel agonists. All the racemic mixtures, with the only exception of the carbamoyl derivatives 9, 12 endowed with scanty solubility, were separated by chiral chromatography into the corresponding enantiomers; the (+) enantiomers were found to be potent agonists while the (-) ones were feeble antagonists. The racemic mixtures were also assessed for their positive inotropic activity on electrically stimulated rat papillary muscle and for their ability to increase Ca(2+) entry into the vascular smooth muscle of rat aorta strips. The cyanofuroxan 8 proved to be an interesting product with dual Ca(2+)-dependent positive inotropic and NO-dependent vasodilating activity.

  6. Implications of Chirality of Drugs and Excipients in Physical Pharmacy.

    Science.gov (United States)

    Duddu, Sarma P.

    1993-01-01

    The interactions of enantiomers of a chiral drug with other chemical entities, which may lead to changes and stereoselective differences in the physicochemical properties of the drug, were investigated. The various interactions described below employed ephedrine, pseudoephedrine and some of their salts, and to a minor extent, propranolol hydrochloride. The interaction of ephedrinium or pseudoephedrinium with the achiral anion, salicylate, yielded crystalline salts with the notable exception of homochiral ephedrine. Racemic ephedrinium salicylate exists as a centrosymmetric crystal (P2_1/n) whereas racemic pseudoephedrinium salicylate is a mixture of homochiral crystals (P2 _1). The inability of ephedrinium to exist as a homochiral salicylate salt is attributed to a high energy conformation of the ephedrinium cation, following conformational analysis. Arising from conformationally favorable interactions, the crystallization of racemic ephedrinium salicylate from aqueous solutions was utilized to improve the enantiomeric purity of a partially resolved mixture of ephedrine from 60% to 82% in one crystallization step. Interaction of the opposite enantiomers of ephedrine and pseudoephedrine in the solid, liquid, solution and vapor state produced the respective racemic compounds. The formation of racemic ephedrine in the solid state as predominantly second order (k = 392 mol^{-1} hr^{-1}), probably mediated by the vapor phase. The formation of racemic pseudoephedrine was predominantly diffusion-controlled in the solid state via an intermediate non-crystalline phase. The interaction with traces of the opposite enantiomer during crystallization of (RS)-(-)-ephedrinium 2-naphthalenesulfonate and (SS)-(+)-pseudoephedrinium salicylate changed pharmaceutically important solid state properties, including dissolution rate. Uptake of the enantiomeric impurity was measured by a new, sensitive HPLC method. The enantiomeric impurity, at mole fractions drug with other chemical

  7. Enantiomer fractions of chlordane components in sediment from U.S. Geological Survey sites in lakes and rivers

    Science.gov (United States)

    Ulrich, E.M.; Foreman, W.T.; Van Metre, P.C.; Wilson, J.T.; Rounds, S.A.

    2009-01-01

    Spatial, temporal, and sediment-type trends in enantiomer signatures were evaluated for cis- and trans-chlordane (CC, TC) in archived core, suspended, and surficial-sediment samples from six lake, reservoir, and river sites across the United States. The enantiomer fractions (EFs) measured in these samples are in good agreement with those reported for sediment, soil, and air samples in previous studies. The chlordane EFs were generally close to the racemic value of 0.5, with CC values ranging from 0.493 to 0.527 (usually >0.5) and TC values from 0.463 to 0.53 (usually <0.5). EF changes with core depth were detected for TC and CC in some cores, with the most non-racemic values near the top of the core. Surficial and suspended sediments generally have EF values similar to the top core layers but are often more non-racemic, indicating that enantioselective degradation is occurring before soils are eroded and deposited into bottom sediments. We hypothesize that rapid losses (desorption or degradation) from suspended sediments of the more bioavailable chlordane fraction during transport and initial deposition could explain the apparent shift to more racemic EF values in surficial and top core sediments. Near racemic CC and TC in the core profiles suggest minimal alteration of chlordane from biotic degradation, unless it is via non-enantioselective processes. EF values for the heptachlor degradate, heptachlor epoxide (HEPX), determined in surficial sediments from one location only were always non-racemic (EF ??? 0.66), were indicative of substantial biotic processing, and followed reported EF trends.

  8. Synthesis of novel glucose-based polymers and their applications as chiral stationary phases for high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Tomoyuki IKAI; Takayuki YAMADA

    2016-01-01

    Two novel polymers containing glucose units as the main-chain that only differ in terms of their regioregularity were synthesized to evaluate their chiral recognition abilities as chiral stationary phases( CSPs) for high performance liquid chromatography( HPLC). The regioregular polymer( poly-5)shows clear resolution ability for the racemate of cobalt(Ⅲ)acetylacetonate( Co( acac)3 ),whereas the corresponding regioirregular polymer(poly-3)does not show any chiral recognition for Co(acac)3. The regioregular polymer main-chain seems to play an important role not only in providing an efficient interaction with the racemate but also in expressing the chiral recognition ability as a CSP for HPLC.

  9. (△,∧)-[Tris (1,10-phenanthroline)Zn(Ⅱ)][(R,S)-6,6'-dibromo-2,2'-dimethoxy-1,1'-binaphthylene-4,4'-disulfonate]%消旋的有机二磺酸三邻菲咯啉锌配合物

    Institute of Scientific and Technical Information of China (English)

    黄雪峰; 钱坤

    2005-01-01

    Compound [Zn (phen)3] [BDA] (1) (BDA =6,6' -dibromo-2,2' -dimethoxy- 1,1' -binaphthylene-4,4' -disulfonate, phen= 1,10-phenanthroline) composes of the anion part (racemic-(R,S)-6,6'-dibromo-2,2'-dimethoxy- 1, 1'binaphthylene-4,4'-disulfonate ) and the cation part which consists of a racemic octahedrally coordinated zinc center defined six nitrogen atoms from three phen rings to form an inorganic chirality that can be resolution by chiral organic ligand, the 3D framework was formed through the strong H-bonding interaction between sulfonate and water. CCDC: 277924.

  10. Chemoenzymatic synthesis and biological evaluation of enantiomerically enriched 1-(β-hydroxypropylimidazolium- and triazolium-based ionic liquids

    Directory of Open Access Journals (Sweden)

    Paweł Borowiecki

    2013-03-01

    Full Text Available Racemic 1-(β-hydroxypropylazoles were prepared by solvent-free direct regioselective ring opening of 1,2-propylene oxide with imidazole or 1,2,4-triazole. Lipase-catalyzed transesterification of alcohols with vinyl acetate resulted in kinetic enantiomers resolution. Separated (S-enantiomers of (+-1-(1H-imidazol-1-ylpropan-2-ol and (+-1-(1H-1,2,4-triazol-1-ylpropan-2-ol were quaternized with alkyl bromides or iodides, yielding novel optically active ionic liquids. Racemic salts were tested against a wide range of microorganisms.

  11. Spontaneous Resolution and Carbonation of Chiral Benzyllithium Complexes

    DEFF Research Database (Denmark)

    Lennartson, Anders; Sundberg, Jonas; Wiklund, Tove

    2010-01-01

    In search for new examples of absolute asymmetric synthesis (AAS), chiral α-substituted benzyllithium complexes have been prepared. While [Li(phet)(pmdta)] (1) (phet = 1-phenylethyl, pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine) affords only racemic crystals, a promising candidate for AAS...... was indeed found: [Li(phet)(tmpda)], α-2, (tmpda = N,N,N′,N′-tetramethylpropylenediamine) crystallises as a conglomerate. Although concomitant polymorphism was not observed, a racemic phase (β-2) could also be isolated. Chiral crystals of α-2 gave 2-phenylpropionic acid in high yield on reaction with gaseous...

  12. Enantioselective synthesis of both (-)-(R)-and (+)-(S)-angustureine controlled by enzymatic resolution

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, Gaspar, E-mail: gaspardm@qui.ufmg.br [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Inst. de Ciencias Exatas. Dept. de Qumica; Diaz, Marisa A.N. [Universidade Federal de Vicosa, MG (Brazil). Dept. de Bioquimica e Biologia Molecular; Reis, Marco A. [Centro Federal de Educacao Tecnologica (CEFET), Belo Horizonte, MG (Brazil). Dept. de Quimica

    2013-09-15

    The present study describes a new synthesis of (-)-(R)- and (+)-(S)-angustureine enantiomers, as well as of racemate ({+-})-angustureine, from a racemic {beta}-amino ester controlled by kinetic enzymatic resolution. This strategy allowed to incorporate the basic skeleton, as well as to control the single stereocenter at carbon 2 in both enantiomers. The sequence of five steps starting from the chiral {beta}-amino ester and sodium carboxylate for the synthesis of both alkaloids achieved overall yields of 80 and 44%, respectively, and produced excellent enantiomeric excesses (95 and 96%, respectively) with no protection of functional groups in any of the steps. (author)

  13. Differential effects of thioridazine enantiomers on action potential duration in rabbit papillary muscle

    DEFF Research Database (Denmark)

    Jensen, A. S.; Pennisi, C. P.; Sevcencu, C.;

    2015-01-01

    with (+)-thioridazine. In this study we for the first time investigate the cardiotoxicity of the isolated thioridazine enantiomers and show their effects on ventricular repolarization. The effects of (+)-thioridazine, (-)-thioridazine, and racemate on the rabbit ventricular action potential duration (APD) were...... investigated in a randomized controlled blinded experiment. Action potentials were measured in papillary muscles isolated from 21 female rabbits, and the drug effect on 90% APD in comparison with control (DeltaDelta-APD90) was evaluated. Increasing concentrations of (+)-thioridazine and the racemate caused...

  14. Complex of Burkholderia cepacia lipase with transition state analogue of 1-phenoxy-2-acetoxybutane: biocatalytic, structural and modelling study.

    Science.gov (United States)

    Luić, M; Tomić, S; Lescić, I; Ljubović, E; Sepac, D; Sunjić, V; Vitale, L; Saenger, W; Kojic-Prodić, B

    2001-07-01

    In a series of four racemic phenoxyalkyl-alkyl carbinols, 1-phenoxy-2-hydroxybutane (1) is enantioselectively acetylated by Burkholderia cepacia (formerly Pseudomonas cepacia) lipase with an E value > or = 200, whereas for the other three racemates E was found to be analogue with a tetrahedral P-atom, (R(P),S(P))-O-(2R)-(1-phenoxybut-2-yl)methylphosphonic acid chloride was prepared and crystallized in complex with B. cepacia lipase. The X-ray structure of the complex was determined, allowing to compare the conformation of the inhibitor with results of molecular modelling.

  15. Enantiomer-Specific State Transfer of Chiral Molecules

    CERN Document Server

    Eibenberger, Sandra; Patterson, David

    2016-01-01

    State-selective enantiomeric excess is realized using microwave-driven coherent population transfer. The method selectively promotes either R- or S- molecules to a higher rotational state by phase-controlled microwave pulses that drive electric-dipole allowed rotational transitions. We demonstrate the method using a racemic mixture of 1,2-propanediol. This method of chiral enrichment can be applied to nearly any chiral molecule that can be vaporized and cooled to the point where rotationally resolved spectroscopy is possible, including molecules that rapidly racemize. The rapid chiral switching demonstrated here allows for new applications in high-precision spectroscopic searches for parity violation in chiral molecules.

  16. Asymmetric syntheses and transformations--tools for chirality multiplication in drug synthesis.

    Science.gov (United States)

    Gawroński, Jacek

    2006-01-01

    A review of currently used methods for the synthesis and resolution of enantiomers of drugs and their precursors is presented. For the synthesis part the methods of diastereoselective as well as enantioselective synthesis are discussed, with particular consideration given to enantioselective catalysis with either metal complexes or biocatalysts. Desymmetrization processes are also included as methods to access enantiomerically pure compounds. Racemate resolution still remains an important method to obtain pure enantiomers and methods involving kinetic resolution in enzymatic or chemical systems, and particularly in connection with racemization (dynamic kinetic resolution) are on the rise in fine chemical industry, when applicable.

  17. Chirality--a new era of therapeutics.

    Science.gov (United States)

    Agrawal, Y K; Bhatt, H G; Raval, H G; Oza, P M; Gogoi, P J

    2007-05-01

    To develop the newer pharmaceuticals and to spur the strong growth, being a general property of 'handedness', chirality plays a major role. The Easson-Stedman principle shows the differences in the biological activity between enantiomers resulted from selective reactivity of one enantiomer with its receptor. It helps to improve the pharmacokinetic properties and to remove undesirable side effects by virtue of the unique activity of enantiomers. Racemic switching and marketing drug combinations are used as tools for drug life-cycle management and to redevelop racemic mixtures as single enantiomers.

  18. Stereoselective Effects of Abused “Bath Salt” Constituent 3,4-Methylenedioxypyrovalerone in Mice: Drug Discrimination, Locomotor Activity, and Thermoregulation

    OpenAIRE

    Gannon, Brenda M.; Williamson, Adrian; Suzuki, Masaki; Rice, Kenner C; Fantegrossi, William E.

    2016-01-01

    3,4-Methylenedioxypyrovalerone (MDPV) is a common constituent of illicit “bath salts” products. MDPV is a chiral molecule, but the contribution of each enantiomer to in vivo effects in mice has not been determined. To address this, mice were trained to discriminate 10 mg/kg cocaine from saline, and substitutions with racemic MDPV, S(+)-MDPV, and R(−)-MDPV were performed. Other mice were implanted with telemetry probes to monitor core temperature and locomotor responses elicited by racemic MDP...

  19. Resolução do ibuprofeno: um projeto para disciplina de química orgânica experimental

    Directory of Open Access Journals (Sweden)

    Adriano L. Romero

    2012-01-01

    Full Text Available A practical and didactic sequence of experiments was proposed to illustrate the stereochemistry concept, optically active compounds, resolution of racemates, and use of the NMR technique, including 2D-COSY for identification of organic compounds, on a laboratory course for undergraduate students. The sequence was: extractions of racemic ibuprofen and chiral naproxen from commercial tablets; syntheses of diastereoisomeric amides reacting chiral (S-(--α-methylbenzylamine with (±-ibuprofen; separation and determination of absolute configuration of amides by ¹H NMR spectroscopy and GC analysis, and hydrolysis of amides to obtain (+- and (--ibuprofen.

  20. Application of a novel method for age estimation of a baleen whale and a porpoise

    DEFF Research Database (Denmark)

    Nielsen, Nynne H.; Garde, Eva; Heide-Jørgensen, Mads Peter

    2013-01-01

    Eyeballs from 121 fin whales (Balaenoptera physalus) and 83 harbor porpoises (Phocoena phocoena) were used for age estimation using the aspartic acid racemization (AAR) technique. The racemization rate (kAsp) for fin whales was established from 15 fetuses (age 0) and 15 adult whales where age was...... ± 0.0018) were estimated, which is considerably higher than found for other cetaceans. Correlation between chosen age estimates from AAR and GLG counts indicated that AAR might be an alternative method for estimating age in marine mammals....

  1. Recent Achievements in Simulated Moving Bed (SMB Technology. Part II

    Directory of Open Access Journals (Sweden)

    Roje, M.

    2010-09-01

    Full Text Available Progress in the method of simulated moving bed (SMB technology and some important achievements in separation of specific classes of racemic compounds of therapeutic interest are reported in the Part I of this review. Part II describes novel methods of SMB technology. Complex technologies,such as the combination of SMB and biocatalytic reactions, and SMB with crystallization process, are presented. VariCol variant of SMB, and its application in the separation of the racemic mixtures of commercial and academic interest are discussed. In the conclusive section, comments are given concerning the economic dimension and the market of enantiomerically pure compounds.

  2. Preparation and Chiral Selectivity of BSA-Modified Ceramic Membrane

    Institute of Scientific and Technical Information of China (English)

    Cai Lian SU; Rong Ji DAI; Bin TONG; Yu Lin DENG

    2006-01-01

    An affinity-transport system, containing porous ceramic membranes bound with bovine serum albumin (BSA) was used for chiral separation of racemic tryptophan. The preparation of BSA modified ceramic membrane included three steps. Firstly, the membrane was modified with amino group using silanization with an amino silane. Secondly, the amino group modified membrane was bound with aldehyde group using gluteraldehyde. Finally, BSA was covalently bound on the surface of the ceramic membrane. Efficient separation of racemic tryptophan was carried out by performing permeation cell experiments, with BSA modified, porous ceramic membranes.

  3. Saponification of esters of chiral alpha-amino acids anchored through their amine function on solid support.

    Science.gov (United States)

    Cantel, Sonia; Desgranges, Stéphane; Martinez, Jean; Fehrentz, Jean-Alain

    2004-06-01

    Anchoring an alpha-amino acid residue by its amine function onto a solid support is an alternative to develop chemistry on its carboxylic function. This strategy can involve the use of amino-acid esters as precursors of the carboxylic function. A complete study on the Wang-resin was performed to determine the non racemizing saponification conditions of anchored alpha-amino esters. The use of LiOH, NaOH, NaOSi(Me)3, various solvents and temperatures were tested for this reaction. After saponification and cleavage from the support, samples were examined through their Marfey's derivatives by reversed phase HPLC to evaluate the percentage of racemization.

  4. Enantioselective pharmacodynamic and pharmacokinetic analysis of two chiral CNS-active carbamate derivatives of valproic acid.

    Science.gov (United States)

    Shekh-Ahmad, Tawfeeq; Mawasi, Hafiz; McDonough, John H; Finnell, Richard H; Wlodarczyk, Bogdan J; Yavin, Eylon; Bialer, Meir

    2014-12-01

    2-Ethyl-3-methylbutyl-carbamate (EMC) and 2-isopropylpentyl-carbamate (IPC) are among the most potent anticonvulsant carbamate derivatives of valproic acid. EMC and IPC are chiral compounds. Consequently, the aim of the current study was to comparatively evaluate the pharmacokinetic (PK) and pharmacodynamic (PD anticonvulsant activity) profile of EMC and IPC individual enantiomers. The anticonvulsant activity of EMC and IPC individual enantiomers was evaluated in several anticonvulsant rodent models including maximal electroshock (MES), 6 Hz psychomotor, subcutaneous (pentylenetetrazole) (scMet), and the pilocarpine-induced and soman-induced status epilepticus (SE). The PK-PD relationship of EMC and IPC individual enantiomers was evaluated following intraperitoneal administration (50 mg/kg) to rats. Induction of neural tube defects (NTDs) was evaluated in a mouse strain that was highly susceptible to teratogen-induced NTDs. In mice and rats, (2S)-EMC exhibited anticonvulsant activity similar to that of racemic EMC in the MES and scMet tests, whereas in the 6 Hz test, racemic EMC was more potent than its two individual enantiomers. Racemic EMC exhibited a potent activity in the soman-induced SE model when administered 5 and 20 min after seizure onset with median effective dose (ED50 ) values of 33 and 48 mg/kg, respectively. (2R)-IPC and (2S)-IPC exhibited ED50 values similar to those of racemic IPC in the mouse and rat MES and scMet models. (2R)-IPC had similar ED50 values on the 6 Hz tests. Racemic IPC had an ED50 value of 107 mg/kg in the pilocarpine-induced SE model when given 30 min after seizure onset. Racemic EMC and IPC and their enantiomers had similar clearance (3.8-5.5 L/h/kg) and short half-life (<1 h). EMC and its enantiomers did not cause NTDs at doses 3-10 times higher than their anticonvulsant ED50 values. EMC and IPC did not exhibit enantioselective PK, a fact that may contribute to their nonenantioselective activity in any of the anticonvulsant

  5. (2S-1,1-Dichloro-2-(2-chlorophenyl-2-(4-chlorophenylethane

    Directory of Open Access Journals (Sweden)

    Lars Eriksson

    2009-02-01

    Full Text Available The title compound, C14H10Cl4, is easily crystallized while the other enantiomorph only forms an oil upon crystallization attempts. The title compound has a considerably higher density, ρ ≃ 1.562 Mg m−3 compared to the racemic substance, ρ ≃ 1.514 Mg m−3. This is supported by the fact there are two intermolecular halogen–halogen contacts in the title compound compared with only one the racemic compound. The dihedral angle between the two phenyl rings is 76.83 (5°

  6. Resolution of ibuprofen: a project for an experimental organic chemistry course; Resolucao do ibuprofeno: um projeto para disciplina de quimica organica experimental

    Energy Technology Data Exchange (ETDEWEB)

    Romero, Adriano L.; Baptistella, Lucia H.B.; Coelho, Fernando; Imamura, Paulo M., E-mail: imam@iqm.unicamp.br [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica

    2012-07-01

    A practical and didactic sequence of experiments was proposed to illustrate the stereochemistry concept, optically active compounds, resolution of racemates, and use of the NMR technique, including 2D-COSY for identification of organic compounds, on a laboratory course for undergraduate students. The sequence was: extractions of racemic ibuprofen and chiral naproxen from commercial tablets; syntheses of diastereoisomeric amides reacting chiral (S)-(-)-{alpha}-methylbenzylamine with (+-)-ibuprofen; separation and determination of absolute configuration of amides by {sup 1}H NMR spectroscopy and GC analysis, and hydrolysis of amides to obtain (+)- and (-)-ibuprofen. (author)

  7. Interactions between CO and Poly(p-phenylene vinylene as Induced by Ion-Exchanged Zeolites

    Directory of Open Access Journals (Sweden)

    Sujitra Wongkasemjit

    2009-12-01

    Full Text Available The effects of zeolite type, ion-exchanged level, and ion type on the electrical conductivity responses of poly(p-phenylene vinylene (PPV, doped poly(p-phenylene vinylene (dPPV and zeolite composites under CO exposures were investigated. The electrical sensitivity of dPPV/Cu+-ZSM5(Si/Al = 23 system shows a negative sensitivity value of −0.154, while the Na+ system gives a positive sensitivity of 1.48. Based on FTIR and TPD data, the positive response of PPV/Na+-ZSM5 stems from the CO molecules acting as a secondary dopant. On the other hand, the negative response of PPV/Cu+-ZSM5 originates from the fact that CO molecules are selectively adsorbed on Cu+ sites rather than C+ sites of doped PPV.

  8. Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

    Science.gov (United States)

    Lee, Kyong-Hwan

    2016-05-01

    Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

  9. Biosensors Based on Nano-Gold/Zeolite-Modified Ion Selective Field-Effect Transistors for Creatinine Detection

    Science.gov (United States)

    Ozansoy Kasap, Berna; Marchenko, Svitlana V.; Soldatkin, Oleksandr O.; Dzyadevych, Sergei V.; Akata Kurc, Burcu

    2017-03-01

    The combination of advantages of using zeolites and gold nanoparticles were aimed to be used for the first time to improve the characteristic properties of ion selective field-effect transistor (ISFET)-based creatinine biosensors. The biosensors with covalently cross-linked creatinine deiminase using glutaraldehyde (GA) were used as a control group, and the effect of different types of zeolites on biosensor responses was investigated in detail by using silicalite, zeolite beta (BEA), nano-sized zeolite beta (Nano BEA) and zeolite BEA including gold nanoparticle (BEA-Gold). The presence of gold nanoparticles was investigated by ICP, STEM-EDX and XPS analysis. The chosen zeolite types allowed investigating the effect of aluminium in the zeolite framework, particle size and the presence of gold nanoparticles in the zeolitic framework.

  10. Synthesis of Fatty Alcohols from Oil Palm Using a Catalyst of Ni-Cu Supported onto Zeolite

    Directory of Open Access Journals (Sweden)

    L. Giraldo

    2010-01-01

    Full Text Available A series of Ni-Cu supported onto zeolite type ZSM-5 has been synthesized by direct hydrothermal method without template agent and characterized using XRD, FT-IR, NRM mass, SEM, CG and N2 adsorption techniques. The catalytic performance of the obtained materials was evaluated and utilized for the hydrogenation of palm oil at 453 K and 40 atmospheres of pressure. The results show that the samples exhibited typical hexagonal arrangement of mesoporous structure with high surface area and the heteroatoms were probably incorporated into the framework of ZSM-5. Catalytic tests show that the bimetallic incorporated materials were effective as catalysts in the hydrogenation of oil palm producing fatty alcohols typical.

  11. Prevention of trace and major element leaching from coal combustion products by hydrothermally-treated coal ash

    Energy Technology Data Exchange (ETDEWEB)

    Adnadjevic, B.; Popovic, A.; Mikasinovic, B. [University of Belgrade, Belgrade (Serbia). Dept. of Chemistry

    2009-07-01

    The most important structural components of coal ash obtained by coal combustion in 'Nikola Tesla A' power plant located near Belgrade (Serbia) are amorphous alumosilicate, alpha-quartz, and mullite. The phase composition of coal ash can be altered to obtain zeolite type NaA that crystallizes in a narrow crystallization field (SiO{sub 2}/Al{sub 2}O{sub 3}; Na{sub 2}O/SiO{sub 2}; H{sub 2}O/Na{sub 2}O ratios). Basic properties (crystallization degree, chemical composition, the energy of activation) of obtained zeolites were established. Coal ash extracts treated with obtained ion-exchange material showed that zeolites obtained from coal ash were able to reduce the amounts of iron, chromium, nickel, zinc, copper, lead, and manganese in ash extracts, thus proving its potential in preventing pollution from dump effluent waters.

  12. 粉煤灰合成沸石的研究进展%Research Progress in the Synthesis of Zeolite from Fly Ash

    Institute of Scientific and Technical Information of China (English)

    赵亚娟; 赵西成; 江元汝

    2009-01-01

    This paper provided an overview on the methodologies for zeolite synthesis from fly ash (FA),and a detailed description of conventional alkaline conversion processes,with special emphasis on the experimental conditions to obtain different zeolite types. Zeolitic products could be obtained from FA by direct conversion and two-step conversion. A review of potential applications of different zeolitic products for waste water was also given. The examination of the data presented by different authors reveals that one of the main potential application of this material is the uptake of heavy metal ions from polluted waste waters. The adsorption capacity was different according to zeolites type. A new direction with zeolite synthesized from FA is gived.%本文综述了用粉煤灰合成沸石的方法,详细叙述了传统碱性溶液下粉煤灰转化成沸石实验过程,强调在不同的实验条件下可以合成不同类型的沸石.粉煤灰合成沸石主要采用两种方法:直接转化法和两步转化法.文中还讲述了不同种类沸石在废水处理中表现出的潜能,根据文献中的实验数据表明从废水中去除重金属离子是沸石的主要性能之一,不同种类的沸石在废水处理中吸附重金属离子能力不同.并为粉煤灰合成沸石提出新的发展方向.

  13. Origin, Microbiology, Nutrition, and Pharmacology of D-Amino Acids

    Science.gov (United States)

    Exposure of food proteins to certain processing conditions induces two major chemical changes: racemization of all L-amino acids (LAA) to D-amino acids (DAA) and concurrent formation of crosslinked amino acids such as lysinoalanine (LAL). The diet contains both processing-induced and naturally-form...

  14. Synthesis and enzymic hydrolysis of an o-alanyl ester of phosphatidyl glycerol

    NARCIS (Netherlands)

    Bonsen, P.P.M.; Haas, Gerard H. de; Deenen, L.L.M. van

    1965-01-01

    A racemic 0-alanyl ester of phosphatidyl glycerol, containing one saturated and one unsaturated fatty acid, was synthesized by a reaction between silver benzyl- (γ-oleoyl-β-palmitoyl)-Dl-[alpha]-glycerol phosphate and DL-[alpha]-iodo-B-tert.-butyl-y-(N-tert.-butoxycarbonyl)-m-alanyl glycerol. The sy

  15. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima

    2011-06-01

    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  16. Biocatalytic Resolution of para-Nitrostyrene Oxide by Resting Cells of Different Aspergillus niger Strains

    Institute of Scientific and Technical Information of China (English)

    金浩; 李祖义; 王清

    2001-01-01

    Biocatalytic resolution of racemic para-nitrostyrene oxide was accomplished by employing the epoxide hydrolases from the whole cells of several Aspergillus niger (A. niger) strains. In the cases investigated, excellent selectivity was achieved with such strains as A, niger 5450, A. niger 5320.

  17. THE ROLE OF S-AMLODIPINE IN ARTERIAL HYPERTENSION THERAPY WITH COMBINATION OF CALCIUM CHANNEL BLOCKERS AND BETA-BLOCKERS

    Directory of Open Access Journals (Sweden)

    M. A. Maksimova

    2013-01-01

    Full Text Available Aim. To study efficacy and safety of calcium channel blocker, S-amlodipine, in combination with β-blocker, atenolol, in patients with arterial hypertension (HT 1-2 degree com- pared to fixed combination of racemic amlodipine and atenolol.Material and methods. Patients (n=31, 7 men and 24 women with HT 1–2 degree were included into the study. The patients were randomized into two groups by the com- binations sequence. Treatment with each combination lasted 4 weeks. Office blood pressure (BP was assessed at baseline and at the end of the treatment periods, possible side effects were registered.Results. All patients completed the study. Both combination of S-amlodipine+atenolol and fixed combination of racemic amlodipine+atenolol reduced systolic (in average, -15.9 and -12.7 mm Hg, respectively and diastolic (in average, -7.3 and -5.3 mmHg, respectively BP significantly. Heart rate also decreased during therapy (in average, -3 and -4 bt/min, respectively. The differences between combinations BP and heart rate effects were not significant. 8 and 16 adverse events were registered during S-amlodipine+atenolol and racemic amlodipine+atenolol therapies, respectively Conclusion. Combination of S-amlodipine+atenolol, as well as combination of racemic amlodipine+atenolol are effective in the treatment of patients with HT 1-2 degree, however combination with S-amlodipine has less number of adverse events.

  18. Study on the Stereoselective Synthesis of Carbapenem Sidechain (2S,4S)-4-Acetylsulphanyl-2-[(S)-1-phenylethylcarbamoyl]-pyrrolidine-1-carboxylic Acid 4-Nitrobenzyl Ester

    Institute of Scientific and Technical Information of China (English)

    Qian LIU; Gang FANG; Li Ping WU; Jian Mei CUI; Xiao Tian LIANG; Song WU

    2004-01-01

    A stereoselective and economic synthesis of the carbapenem sidechain (2S, 4S)-4-ace-tylsulphanyl-2-[ (S)1-phenylethyl-carbamoyl] pyrrolidine-l-carboxylic acid 4-nitrobenzyl ester was developed. Due to the effect of spatial hindrance, only the (2S,4S) diastereomer 3 was obtained by coupling 1 and the inexpensive racemic 2 catalyzed by EEDQ.

  19. Total synthesis of aeruginosin 98B.

    Science.gov (United States)

    Trost, Barry M; Kaneko, Toshiyuki; Andersen, Neil G; Tappertzhofen, Christoph; Fahr, Bruce

    2012-11-21

    The first total synthesis of aeruginosin 98B was accomplished. The key step is a highly diastereoselective Pd-catalyzed intramolecular asymmetric allylic alkylation reaction of a diastereomeric mixture of allylic carbonates that is enabled by the use of racemic phosphine ligand L1.

  20. Reversible and irreversible emergence of chiroptical signals in J-aggregates of achiral 4-sulfonatophenyl substituted porphyrins: intrinsic chirality vs. chiral ordering in the solution.

    Science.gov (United States)

    Arteaga, Oriol; El-Hachemi, Zoubir; Canillas, Adolf; Crusats, Joaquim; Rovira, Meritxell; Ribó, Josep M

    2016-09-18

    Mueller matrix polarimetry distinguishes the different origins of the reversible and irreversible chiroptical effects emerging in stirred solutions of J-aggregate nanoparticles: the reversible effect is due to an anisotropic ordering in the solution and the irreversible one is due to a bias from the racemic composition of intrinsically chiral structures.

  1. Nyssaceae

    NARCIS (Netherlands)

    Wasscher, J.

    1948-01-01

    Dioecious trees or shrubs. Leaves simple, scattered. Stipules O. Flowers unisexual, often in heads, in the axils of a bract and with 2 bracteoles. ♂: in axillary heads or short racemes; calyx entire or 5-toothed; petals 5, imbricate, often small, alternate with the calyx; stamens 8-16 in 2 alternati

  2. New leads to resolutions : the family approach

    NARCIS (Netherlands)

    Afraz, Marcel Cyrus

    2003-01-01

    The thesis is about the resolution of racemates, which is still the most convenient and commonly applied method to obtain optically pure products, both in the fine-chemical industry and in the laboratory. From an industrial point of view classical resolution using diastereomeric salts still represen

  3. Demography of Oenocarpus bataua and implications for sustainable harvest of its fruit in western Amazon

    DEFF Research Database (Denmark)

    Isaza, Carolina; Matorrell, C; Cevallos, G;

    2016-01-01

    Oenocarpus bataua is one of the most abundant and most used palm in the Amazon region. The main resource obtained from the species is the fruits that are harvested for human consumption. Across its distribution area adults are felled to obtain the racemes, which may affect the palm’s populations....

  4. Efficient hydrogenation of biomass-derived cyclic di-esters to 1,2-diols.

    Science.gov (United States)

    Balaraman, Ekambaram; Fogler, Eran; Milstein, David

    2012-01-28

    The unprecedented homogeneous hydrogenation of cyclic di-esters, in particular biomass-derived glycolide and lactide, to the corresponding 1,2-diols is catalyzed by Ru(II) PNN (1) and Ru(II) CNN (2) pincer complexes under mild hydrogen pressure and (in the case of 1) neutral conditions. No racemization was observed when a chiral di-ester was used.

  5. The Chiral Bilayer Effect Stabilizes Micellar Fibers

    NARCIS (Netherlands)

    Fuhrhop, Jürgen-Hinrich; Schnieder, Peter; Rosenberg, Jörg; Boekema, Egbert

    1987-01-01

    Dihelical fibers several micrometers in length and gels were obtained by spontaneous aggregation of octyl L- and D-gluconamides. The single strands have the thickness of a bimolecular layer. No fibers are formed from the racemate. The tendency of the chiral amphiphiles to aggregate to very long fibe

  6. Synthesis and enzymic hydrolysis of an o-alanyl ester of phosphatidyl glycerol

    NARCIS (Netherlands)

    Bonsen, P.P.M.; Haas, Gerard H. de; Deenen, L.L.M. van

    1965-01-01

    A racemic 0-alanyl ester of phosphatidyl glycerol, containing one saturated and one unsaturated fatty acid, was synthesized by a reaction between silver benzyl- (γ-oleoyl-β-palmitoyl)-Dl-[alpha]-glycerol phosphate and DL-[alpha]-iodo-B-tert.-butyl-y-(N-tert.-butoxycarbonyl)-m-alanyl glycerol. The sy

  7. Enantio-alteration of gene transcription associated with bioconcentration in adult zebrafish (Danio rerio) exposed to chiral PCB149

    Science.gov (United States)

    Chai, Tingting; Cui, Feng; Mu, Pengqian; Yang, Yang; Xu, Nana; Yin, Zhiqiang; Jia, Qi; Yang, Shuming; Qiu, Jing; Wang, Chengju

    2016-01-01

    Enantioselective enrichment of chiral PCB149 (2,2’,3,4’,5’,6-hexachlorobiphenyl) was analysed in adult zebrafish (Danio rerio) exposed to the racemate, (‑)-PCB149, and (+)-PCB149. Greater enrichment of (‑)-PCB149 compared to (+) PCB149 was observed following 0.5 ng/L exposure; however, as the exposure time and concentration increased, racemic enrichment was observed in adult fish exposed to the racemate. No biotransformation between the two isomers was observed in fish exposed to single enantiomers. When zebrafish were exposed to different forms of chiral PCB149, enantioselective expression of genes associated with polychlorinated biphenyls (PCBs) was observed in brain and liver tissues and enantioselective correlations between bioconcentration and target gene expression levels were observed in brain and liver tissues. The strong positive correlations between expression levels of target genes (alox5a and alox12) and PCB149 bioconcentration suggest that prolonged exposure to the racemate of chiral PCB149 may result in inflammation-associated diseases. Prolonged exposure to (‑)-PCB149 may also affect metabolic pathways such as dehydrogenation and methylation in the brain tissues of adult zebrafish. Hepatic expression levels of genes related to the antioxidant system were significantly negatively correlated with bioconcentration following exposure to (+)-PCB149.

  8. Stackhousiaceae

    NARCIS (Netherlands)

    Brouwer, F.I.

    1948-01-01

    Annual, or perennial herbs with a rhizome. Leaves scattered, entire. Stipules 0 or very small. Racemes terminal. Flowers bisexual, regular, 5-merous, in groups in the axils of bracts. Sepals usually more or less connate, rarely free. Corolla perigynous or almost hypogynous, petals long-clawed, rarel

  9. Quiralidade em moléculas e cristais Chirality at molecules and crystals

    Directory of Open Access Journals (Sweden)

    Ayres Guimarães Dias

    2009-01-01

    Full Text Available The present contribution describes some concepts of stereochemistry and chirality in molecules and crystals. This paper also reports on the development of a simple and fast experiment to prepare and recognize conglomerate and true racemate of tartaric acid produced by mechanic mixture of commercial enantiomers and recristalization. Optical activity and melting point of mixtures are also used in the analysis.

  10. Oxazolidinone Synthesis through Halohydrin Dehalogenase-Catalyzed Dynamic Kinetic Resolution

    NARCIS (Netherlands)

    Mikleusevic, Ana; Hamersak, Zdenko; Salopek-Sondi, Branka; Tang, Lixia; Janssen, Dick B.; Elenkov, Maja Majeric

    2015-01-01

    An efficient dynamic kinetic resolution protocol using a single enzyme is described. Both the kinetic resolution and substrate racemization are catalyzed by halohydrin dehalogenase from Agrobacterium radiobacter AD1 (HheC). The HheC-catalyzed reaction of epibromohydrin and

  11. Dynamic Kinetic Resolution of 2-Phenylpropanal Derivatives to Yield β-Chiral Primary Amines via Bioamination

    NARCIS (Netherlands)

    Fuchs, C.S.; Hollauf, M.; Meissner, M.; Simon, R.C.; Besset, T.; Reek, J.N.H.; Riethorst, W.; Zepeck, F.; Kroutil, W.

    2014-01-01

    The amination of racemic alpha-chiral aldehydes, 2-phenylpropanal derivatives, was investigated employing omega-transaminases. By medium and substrate engineering the optical purity of the resulting β-chiral chiral amine could be enhanced to reach optical purities up to 99% ee. Using enantiocompleme

  12. Ultrasound assisted synthesis of 5,9-dimethylpentadecane and 5,9-dimethylhexadecane--the sex pheromones of Leucoptera coffeella.

    Science.gov (United States)

    Doan, Nhuan Ngoc; Le, Thach Ngoc; Nguyen, Hao Cong; Hansen, Poul Erik; Duus, Fritz

    2007-08-28

    Racemic 5,9-dimethylpentadecane and 5,9-dimethylhexadecane, the major and minor constituents, respectively, of the sex pheromone of Leucoptera coffeella, have been synthesized from citronellol in 56-58% overall yield through six steps. Ultrasound irradiation efficiently supported tosylation of alcohols (two steps) as well as the subsequent cross coupling reactions with the pertinent Grignard reagents (also two steps).

  13. Attempt to Resolute Chiral Clusters by Optically Active Hydrazide

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A new kind of hydrazone (I) diastereoisomers was prepared with enantiomeric hydazide (II) and chiral cluster (III), which was characterized by HMBC. Unfortunately, the mixture could not be separated into pure diastereoisomer. This could be a direction to separate the racemic chiral clusters.

  14. Consecutive dynamic resolutions of phosphine oxides

    NARCIS (Netherlands)

    Kortmann, Felix A.; Chang, Mu Chieh; Otten, Edwin; Couzijn, Erik P A; Lutz, Martin; Minnaard, Adriaan J.

    2014-01-01

    A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio- and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides. © 2014 The Royal Society o

  15. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.;

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...

  16. Jamesbrittenia bergae (Scrophulariaceae, a distinctive new species from Limpopo, South Africa

    Directory of Open Access Journals (Sweden)

    P. Lemmer

    2003-12-01

    Full Text Available Jamesbrittenia bergae P.Lemmer is a new species from the Farm Brakvallei near Thabazimbi in Limpopo [Northern Province]. Large, medium-textured. bright scarlet flowers w ith yellow throats are borne singly in upper leaf axils; the flowering branches, although terminal, do not form elongated racemes: leaves are greyish green, coarsely serrated. It grows in full sun on ferricrete outcrops.

  17. Detection of zinc ions under aqueous conditions using chirality assisted solid-state fluorescence of a bipyridyl based fluorophore.

    Science.gov (United States)

    Sreejith, Sivaramapanicker; Divya, Kizhumuri P; Ajayaghosh, Ayyappanpillai

    2008-07-07

    A pyrrole end-capped bipyridyl ligand incorporating a chiral handle exhibited high solid-state emission when compared to the achiral analogue 1b and to the racemic molecule 1c which allowed the design of a reusable fluorescent probe for the selective detection of Zn2+ under aqueous conditions.

  18. Enzymatic Resolution of 1-Phenylethanol and Formation of a Diastereomer: An Undergraduate [superscript 1]H NMR Experiment to Introduce Chiral Chemistry

    Science.gov (United States)

    Faraldos, Juan A.; Giner, Jos-Luis; Smith, David H.; Wilson, Mark; Ronhovde, Kyla; Wilson, Erin; Clevette, David; Holmes, Andrea E.; Rouhier, Kerry

    2011-01-01

    This organic laboratory experiment introduces students to stereoselective enzyme reactions, resolution of enantiomers, and NMR analysis of diastereomers. The reaction between racemic 1-phenylethanol and vinyl acetate in hexane to form an ester is catalyzed by acylase I. The unreacted alcohol is then treated with a chiral acid and the resulting…

  19. Synthesis of 3,4-Dibenzyltetrahydrofuran Lignans (9,9′-Epoxylignanes

    Directory of Open Access Journals (Sweden)

    Kristiina Wähälä

    2013-10-01

    Full Text Available Different strategies for the racemic or enantiospecific total syntheses of plant and mammalian 3,4-dibenzyltetrahydrofuran lignans are reviewed and compared. The multi-step approaches have various key step strategies: Diels–Alder reactions, Stobbe condensations, Michael additions, alkylations, nitrile oxide cycloadditions, radical cyclisations, dianion and oxidative couplings.

  20. Genetic diversity in Brassica species and Eruca sativa for yield associated parameters

    Directory of Open Access Journals (Sweden)

    Kanwal Mahwish

    2014-01-01

    Full Text Available Brassica species are vulnerable to narrow genetic base due to the ignorance of their wild relatives which possess many superior characters. This study was aimed to explore the genetic diversity in five Brassica species from U triangle as well as in their wild relative Eruca sativa. For the complete insight of genetic diversity, four accessions, each from five species of genus Brassica along with one species of Eruca collected from different geographical locations (exotic and indigenous were selected. Six yield associated parameters viz., primary branches plant-1, plant height, main raceme length, silique length, silique width and silique main raceme-1 were studied. Highly significant variations among all species were observed. Mean performance showed that wild relative E. sativa was superior for primary branches plant -1 and plant height, which are the main yield associated traits. In case of Brassica species, B. campestris gave the lengthiest main racemes, B. nigra produced more silique main raceme-1 and B. carinata produced the longest and widest silique.

  1. Monitoring molecular chirality exchange by photon echoes

    Directory of Open Access Journals (Sweden)

    Mukamel Shaul

    2013-03-01

    Full Text Available We construct pulse polarization configurations in heterodyne four wave mixing for monitoring ultrafast(picosecondexchange rates between optical isomers with axial chirality.This information is not available from linear circular dichroism,since enantiomers may not be isolated and racemate shows no chiral signal.

  2. Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs.

    Science.gov (United States)

    Morgan, Ian R; Di Paolo, Angela; Vidovic, Dragoslav; Fallis, Ian A; Aldridge, Simon

    2009-12-21

    A facile synthetic approach is reported for the synthesis of dissymmetric 1,2-ferrocenediyl Lewis acids and mixed acid-base pairs including the first example of a 1-phosphino-2-borylferrocene; the use of non-racemic electrophiles allows for the isolation of single diastereomer products.

  3. The biodegradability of EDDHA chelates under calcareous soil conditions

    NARCIS (Netherlands)

    Schenkeveld, W.D.C.; Hoffland, E.; Reichwein, A.M.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2012-01-01

    FeEDDHA (iron (3 +) ethylenediamine-N,N'-bis(hydroxy phenyl acetic acid) products are commonly applied to mend or prevent Fe chlorosis in plants. In soil application, racemic and meso o,o-FeEDDHA are the effective components, while o,p-FeEDDHA tends to adsorb or react to o,p-CuEDDHA. Upon

  4. The Enantiomer Separations of Allethrone and Propargyllone Using Two Long Chain Acylated β-Cyclodextrin Derivatives as CGC Capillary Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Using two β-cyclodextrin derivatives (CDs) with long chain of acyl groups as chiral stationary phases (CSPs) of capillary gas chromatography (CGC), the enantiomers of racemic allethrone and propargyllone were well resolved after derived with acetyl chloride. The enantiomer excess values (e.e.%) of 1S-allethrone and 1S-propargyllone were also determined successfully using these CDs.

  5. The behaviour of EDDHA isomers in soils as influenced by soil properties.

    NARCIS (Netherlands)

    Schenkeveld, W.D.C.; Reichwein, A.M.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2007-01-01

    FeEDDHA products are applied to correct iron chlorosis in plants and consist of a mixture of EDDHA isomers chelated to iron. In this study such mixtures have been divided into four (groups of) isomers: racemic o,o-EDDHA, meso o,o-EDDHA, o,p-EDDHA and rest-EDDHA. The physical and chemical properties

  6. Studies on inclusion resolution : gaining insight into chemical and physical properties

    NARCIS (Netherlands)

    Müller, Simona

    2003-01-01

    Inclusion is a process where two or more compounds crystallise together in a mixed, but regular, crystal lattice. Inclusion resolution is a relatively new way for separating enantiomers from a racemic mixture which employs inclusion with enantiopure compounds as hosts. An enantiopure host compound

  7. Diastereoselective Hydrogenation and Kinetic Resolution of Imines Using Rhodium/Diphosphine Catalyzed Hydrogenation.

    NARCIS (Netherlands)

    Lensink, Cornelis; Vries, Johannes G. de

    1993-01-01

    Kinetic resolution of racemic α-methylbenzyl amine can be achieved with 98% ee. of the remaining amine at 70% conversion using the Rhodium/2S,4S-BDPP catalyzed asymmetric hydrogenation of imines. The same catalyst will hydrogenate optically pure α-methylbenzyl amines with a diastereoselectivity of u

  8. [Antimicrobial activity of Calendula L. plants].

    Science.gov (United States)

    Radioza, S A; Iurchak, L D

    2007-01-01

    The sap of different organs of genus Calendula plant species has been studied for antimicrobial activity. The sap of racemes demonstrated the most expressed antimicrobial effect while that of the roots - the least one. Calendula species inhibited all tested pathogenic microorganisms, especially Pseudomonas syringae, P. fluorescens, Xanthomonas campestris, Agrobacterium tumefaciens. Calendula suffruticosa was the most active to all investigated microorganisms.

  9. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents.

    Science.gov (United States)

    Mutti, Francesco G; Orthaber, Andreas; Schrittwieser, Joerg H; de Vries, Johannes G; Pietschnig, Rudolf; Kroutil, Wolfgang

    2010-11-14

    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to enantioenriched chlorohydrins via an oxidation-asymmetric reduction sequence.

  10. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

    NARCIS (Netherlands)

    Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang

    2010-01-01

    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to enantioenrich

  11. Domain Modeling: NP_001997.5 [SAHG[Archive

    Lifescience Database Archive (English)

    Full Text Available NP_001997.5 chr4 Snow Flea Antifreeze Protein Quasi-racemate p2pnea_ chr4/NP_001997.5/NP_001997.5..._apo_27-110.pdb p3boga_ chr4/NP_001997.5/NP_001997.5_holo_27-110.pdb swppa 33P,34G,36A,60A,61G

  12. Differential Toxicity and Accumulation of Fipronil Enantiomers in the Fathead Minnow (Pimephales promelas)

    Science.gov (United States)

    Fipronil is a chiral insecticide applied as a racemate of two enantiomers. Because of its high log Koc, fipronil will be found primarily in sediments of aquatic environments. Although a number of studies have examined toxicity in aquatic invertebrates, data on enantioselective t...

  13. Meeting in China: Differential Toxicity and Accumulation of Fipronil Enantiomers in the Fathead Minnow (Pimephales promelas)

    Science.gov (United States)

    Fipronil is a chiral insecticide applied as a racemate with two enantiomers. Because of its high log KOC, fipronil will be found primarily in sediments of aquatic environments. Although a number of studies have examined toxicity in aquatic invertebrates, data on enantioselective...

  14. ACUTE AND CHRONIC EFFECTS OF FIPRONIL AND ITS ENANTIOMERS TO AQUATIC ORGANISMS

    Science.gov (United States)

    Fipronil is a phenylpyrazole insecticide used in agriculture and domestic settings for controlling various insect pests in crops, lawns and residential structures. Fipronil is chiral; however, it is released into the environment as a racemic mixture of two enantiomers. In this st...

  15. TOXICITY OF FIPRONIL AND ITS ENANTIOMERS TO MARINE AND FRESHWATER NON-TARGETS

    Science.gov (United States)

    Fipronil is a phenylpyrazole insecticide used in agricultural and domestic settings for controlling various insect pests in crops, lawns, and residential structures. Fipronil is chiral; however, it is released into the environment as a racemic mixture of two enantiomers. In this ...

  16. ENANTIOSELECTIVE CHRONIC TOXICITY OF FIPRONIL TO CERIODAPHNIA DUBIA

    Science.gov (United States)

    Fipronil is a phenylpyrazole pesticide that has greatly increased in popularity in recent years. As a chiral molecule, fipronil is released into the environment as a 1:1 mixture (called a racemate) of its two enantiomers. Previous toxicity work has indicated that the enantiomer...

  17. Domain Modeling: NP_002211.1 [SAHG[Archive

    Lifescience Database Archive (English)

    Full Text Available NP_002211.1 chr15 Snow Flea Antifreeze Protein Quasi-racemate p2pnea_ chr15/NP_002211.1/NP_002211....1_apo_63-142.pdb p3boga_ chr15/NP_002211.1/NP_002211.1_holo_63-142.pdb swppa 69G,70L,72R,93P,

  18. Chirality emergence in thin solid films of amino acids by polarized light from synchrotron radiation and free electron laser.

    Science.gov (United States)

    Takahashi, Jun-ichi; Shinojima, Hiroyuki; Seyama, Michiko; Ueno, Yuko; Kaneko, Takeo; Kobayashi, Kensei; Mita, Hajime; Adachi, Mashahiro; Hosaka, Masahito; Katoh, Masahiro

    2009-07-07

    One of the most attractive hypothesis for the origin of homochirality in terrestrial bioorganic compounds is that a kind of "chiral impulse" as an asymmetric excitation source induced asymmetric reactions on the surfaces of such materials such as meteorites or interstellar dusts prior to the existence of terrestrial life (Cosmic Scenario). To experimentally introduce chiral structure into racemic films of amino acids (alanine, phenylalanine, isovaline, etc.), we irradiated them with linearly polarized light (LPL) from synchrotron radiation and circularly polarized light (CPL) from a free electron laser. After the irradiation, we evaluated optical anisotropy by measuring the circular dichroism (CD) spectra and verified that new Cotton peaks appeared at almost the same peak position as those of the corresponding non-racemic amino acid films. With LPL irradiation, two-dimensional anisotropic structure expressed as linear dichroism and/or linear birefringence was introduced into the racemic films. With CPL irradiation, the signs of the Cotton peaks exhibit symmetrical structure corresponding to the direction of CPL rotation. This indicates that some kinds of chiral structure were introduced into the racemic film. The CD spectra after CPL irradiation suggest the chiral structure should be derived from not only preferential photolysis but also from photolysis-induced molecular structural change. These results suggest that circularly polarized light sources in space could be associated with the origin of terrestrial homochirality; that is, they would be effective asymmetric exciting sources introducing chiral structures into bio-organic molecules or complex organic compounds.

  19. Dynamic control and amplification of molecular chirality by circular polarized light

    NARCIS (Netherlands)

    Huck, N.P.M.; Jager, W.F.; de Lange, B.; Feringa, B.L.

    1996-01-01

    The enantiomers of a racemic photoresponsive material represent two distinct states that can be modulated with irradiation at a single wavelength by changing the handedness of the light, Dynamic control over molecular chirality was obtained by the interconversion of enantiomers of helically shaped m

  20. Cloning and application of epoxide hydrolases from yeasts

    NARCIS (Netherlands)

    Visser, J.H.

    2002-01-01

    Epoxides are cyclic ethers that readily react with various nucleophilic compounds. Consequently, epoxides can be used in many chemical synthesis reactions. Two enantiomeric forms of an epoxide are possible if one of the carbon atoms is chiral. This means that the epoxide is actually a racem

  1. Differential psychopathology and patterns of cerebral glucose utilisation produced by (S)- and (R)-ketamine in healthy volunteers using positron emission tomography (PET)

    NARCIS (Netherlands)

    Vollenweider, FX; Leenders, KL; Oye, [No Value; Hell, D; Angst, J

    Until recently, racemic ketamine (S-ketamine/R-ketamine=50:50) has been used to study NMDA receptor hypofunction in relation to pathophysiological models of schizophrenia. Ketamine given to normal humans in subanesthetic doses produces a model psychosis including both positive and negative symptoms

  2. A Concise Access to C2-Symmetric Chiral 4-Pyrrolidinopyridine Catalysts with Dual Functional Side Chains.

    Science.gov (United States)

    Mishiro, Kenji; Takeuchi, Hironori; Furuta, Takumi; Kawabata, Takeo

    2016-07-01

    A practical method was developed for the preparation of a diastereomeric library of C2-symmetric chiral 4-pyrrolidinopyridine catalysts with dual amide side chains. Use of a racemic precursor is the key to the concise production of catalysts with diverse stereochemisty.

  3. Comparative anticonvulsant potency and pharmacokinetics of (+)-and (-)-enantiomers of stiripentol.

    Science.gov (United States)

    Shen, D D; Levy, R H; Savitch, J L; Boddy, A V; Tombret, F; Lepage, F

    1992-06-01

    The anticonvulsant potency and pharmacokinetics of the enantiomers of stiripentol were compared using the intravenous pentylenetetrazol infusion seizure model in the rat. Enantioselectivity was observed with respect to both the anticonvulsant activity and elimination kinetics of this compound. (+)-Stiripentol was 2.4 times more potent than its antipode against pentylenetetrazol-induced clonic seizure (brain EC50 of 15.2 micrograms/ml versus 36.1 micrograms/ml). The (+)-enantiomer was eliminated more rapidly than the (-)-enantiomer, as reflected in a higher plasma clearance (1.64 l/h/kg versus 0.557 l/h/kg) and a shorter half-life (2.83 h versus 6.50 h). Parallel studies with the racemate of stiripentol indicated that the anticonvulsant potency of the racemate was between the potency of the two enantiomers, suggesting that the combined activity reflects the additive action of (+)- and (-)-stiripentol. However, a marked metabolic interaction between enantiomers was evident after racemate administration. These results point to the need for information on the differential pharmacokinetics of stiripentol enantiomers following racemic drug administration.

  4. Chronology of a Difficult Synthesis

    Science.gov (United States)

    Menger, Fredric M.; Sorrells, Jennifer L.

    2009-01-01

    This article describes a short synthesis and many of the difficulties experienced while carrying it out (e.g., low yields, impurities, racemization, nonrepeatable literature preps, etc.). As such, students will be educated in aspects of synthetic organic chemistry that are often down-played, or even not mentioned, in published syntheses. (Contains…

  5. Anion size control of the packing in the metallic versus semiconducting chiral radical cation salts (DM-EDT-TTF)2XF6 (X = P, As, Sb).

    Science.gov (United States)

    Pop, Flavia; Auban-Senzier, Pascale; Canadell, Enric; Avarvari, Narcis

    2016-10-13

    Control of the structural type in metallic enantiopure and racemic radical cation salts is achieved through hydrogen bonding interactions between the chiral donor DM-EDT-TTF and the XF6 anions (X = P, As, Sb), determined by the anion size and the chiral information.

  6. N-Phenyladamantane-1-sulfinamide

    Directory of Open Access Journals (Sweden)

    Mrityunjoy Datta

    2008-08-01

    Full Text Available In the racemic title compound, C16H21NOS, the molecules are packed into polymeric chains in the b-axis direction and are linked along the b axis by N—H...O and C—H...O hydrogen bonds.

  7. Enantioselective hydrolysis of epichlorohydrin using whole Aspergillus niger ZJB-09173 cells in organic solvents

    Indian Academy of Sciences (India)

    Huo-Xi Jin; Zhong-Ce Hu; Yu-Guo Zheng

    2012-09-01

    The enantioselective hydrolysis of racemic epichlorohydrin for the production of enantiopure ()-epichloro-hydrin using whole cells of Aspergillus niger ZJB-09173 in organic solvents was investigated. Cyclohexane was used as the reaction medium based on the excellent enantioselectivity of epoxide hydrolase from A. niger ZJB-09173 in cyclohexane. However, cyclohexane had a negative effect on the stability of epoxide hydrolase from A. niger ZJB-09173. In the cyclohexane medium, substrate inhibition, rather than product inhibition of catalysis, was observed in the hydrolysis of racemic epichlorohydrin using A. niger ZJB-09173. The racemic epichlorohydrin concentration was markedly increased by continuous feeding of substrate without significant decline of the yield. Ultimately, 18.5% of ()-epichlorohydrin with 98% enantiomeric excess from 153.6 mM of racemic epichlorohydrin was obtained by the dry cells of A. niger ZJB-09173, which was the highest substrate concentration in the production of enantiopure ()-epichlorohydrin by epoxide hydrolases using an organic solvent medium among the known reports.

  8. A short synthesis of (+/-)-cytisine.

    Science.gov (United States)

    Botuha, Candice; Galley, Carl M S; Gallagher, Timothy

    2004-07-07

    The synthesis of racemic cytisine has been completed using (i)N-selective alkylation of 6-bromopyridone with bromide and (ii) Pd(0) mediated intramolecular alpha-arylation of lactam as key steps to achieve rapid assembly of the tricyclic core skeleton of the lupin alkaloids.

  9. Total synthesis of (+/-)-cytisine via the intramolecular heck cyclization of activated N-alkyl glutarimides.

    Science.gov (United States)

    Coe, J W

    2000-12-28

    [reaction:see text] A synthesis of racemic cytisine 1 has been developed utilizing an intramolecular Heck cyclization to prepare the bridged tricyclic intermediate 2. The cyclization employs activated glutarimide-derived ketene aminals 3 (X = P(O)OEt(2) or SO(2)CF(3)) and represents the first use of such intermediates in metal-catalyzed processes.

  10. Racisme - et psykologisk perspektiv

    DEFF Research Database (Denmark)

    Singla, Rashmi; Busch-Jensen, Peter

    2007-01-01

    Racisme forstås traditionelt som diskrimination og eksklusion af grupper eller individer ud fra forestillinger om, at mennesker tilhører forskellige racer, der kan rangordnes. I denne betydning indebærer racisme altså en ide om, at mennesket findes i forskellige racemæssige udgaver, karakterisere...

  11. MOLECULARLY IMPRINTED POLYMER TECHNOLOGY: A ...

    African Journals Online (AJOL)

    dell

    Salbutamol (2-(hydroxymethyl)-4-[1-hydroxy-2-(tert-butylamino)ethyl]phenol) ... dimethylamino-3-methyl-1,2-diphenyl-butan-2-yl]propanoate) is an anti-cough agent. ... Efficacy of (S)-omeprazole over the racemic mixture is claimed. .... simultaneous exclusion of sulphur dioxide. ... thermal stability, which affords sterilization.

  12. Nucleophilic addition to an achiral dehydroalanine Schiff base Ni(II) complex as a route to amino acids. A case of stereodetermining asymmetric protonation in the presence of TADDOL

    NARCIS (Netherlands)

    Belokon, Yuri N.; Harutyunyan, Syuzanna; Vorontsov, Evgeni V.; Peregudov, Alexander S.; Chrustalev, Viktor N.; Kochetkov, Konstantin A.; Pripadchev, Dmitriy; Sagyan, Ashot S.; Beck, Albert K.; Seebach, Dieter

    2004-01-01

    We describe herein the elaboration of a new type of a substrate based on the Ni(II) complex of a Schiff base of dehydroalanine, 1, and Michael addition of nucleophiles to it, leading to the synthesis of racemic α-amino acids. We have also developed a catalytic method for the asymmetric 1,4 conjugate

  13. Novel carbohydrate-based chiral ammonium ionic liquids derived from isomannide

    DEFF Research Database (Denmark)

    Kumar, Vineet; Pei, Cao; Olsen, Carl E.

    2008-01-01

    This report describes the synthesis and characterization of novel carbohydrate-based chiral ammonium ionic liquids using isomannide as a biorenewable substrate. The diastereomeric interactions of these chiral ammonium ionic liquids with racemic Mosher's acid salt have been studied using NMR, whic...

  14. Synthesis and preliminary evaluation of (R,S)-1-[2-((carbamoyl-4-hydroxy)phenoxy)-ethylamino]-3-[4-(1-[11C]-met hyl-4-trifluoromethyl-2-imidazolyl)phenoxy]-2-propanol ([11C]CGP 20712A) as a selective beta 1-adrenoceptor ligand for PET

    NARCIS (Netherlands)

    Elsinga, P H; Van Waarde, A; Visser, Gerben; Vaalburg, W

    1994-01-01

    The most selective beta 1-adrenoceptor ligand known at this moment is (S)-1-[2-((carbamoyl-4-hydroxy) phenoxy)ethylamino]-3-[4-(1-methyl-4-trifluoromethyl-2-imidazolyl) phenoxy]-2-propanol (CGP 26505), the S-isomer of CGP 20712A. We prepared the racemic 11C analogue by methylation with [11C]CH3I of

  15. High temperature sublimation of α-amino acids: a realistic prebiotic process leading to large enantiomeric excess.

    Science.gov (United States)

    Tarasevych, Arkadii V; Sorochinsky, Alexander E; Kukhar, Valery P; Guillemin, Jean-Claude

    2015-04-25

    The reiterative high temperature co-sublimation of an enantiopure or an enantioenriched α-amino acid mixed with racemic α-amino acids leads to deracemization of the latter. A synergistic effect is observed for complex mixtures, and the sense of the handedness is, for all compounds, identical to that of the enantioenriched starting material.

  16. An alternative synthesis of (+ - propranolol and (+ – atenolol

    Directory of Open Access Journals (Sweden)

    Aphiwat Teerawutgulrag

    2012-10-01

    Full Text Available Herein, a simple synthesis pathway of beta-blockers starting from allyl amine ispresented. This synthesis features the opening of an epoxide ring with phenol derivatives followed by N-alkylation with iso-propylbromide to produce racemic propranolol and atenolol.

  17. Synthesis and preliminary evaluation of (R,S)-1-[2-((carbamoyl-4-hydroxy)phenoxy)-ethylamino]-3-[4-(1-[11C]-met hyl-4-trifluoromethyl-2-imidazolyl)phenoxy]-2-propanol ([11C]CGP 20712A) as a selective beta 1-adrenoceptor ligand for PET

    NARCIS (Netherlands)

    Elsinga, P H; Van Waarde, A; Visser, Gerben; Vaalburg, W

    The most selective beta 1-adrenoceptor ligand known at this moment is (S)-1-[2-((carbamoyl-4-hydroxy) phenoxy)ethylamino]-3-[4-(1-methyl-4-trifluoromethyl-2-imidazolyl) phenoxy]-2-propanol (CGP 26505), the S-isomer of CGP 20712A. We prepared the racemic 11C analogue by methylation with [11C]CH3I of

  18. An alternative synthesis of (+) - propranolol and (+) – atenolol

    OpenAIRE

    Aphiwat Teerawutgulrag

    2012-01-01

    Herein, a simple synthesis pathway of beta-blockers starting from allyl amine ispresented. This synthesis features the opening of an epoxide ring with phenol derivatives followed by N-alkylation with iso-propylbromide to produce racemic propranolol and atenolol.

  19. Dramatic Substituent Effect on the CCL-catalyzed Kinetic Resolution of 1-Aryl-2,3-allenols

    Institute of Scientific and Technical Information of China (English)

    XU, Dai-Wang(徐代旺); LI, Zu-Yi(李祖义); MA, Sheng-Ming(麻生明)

    2004-01-01

    Optically active 1-aryl-2,3-allenols were obtained via CCL-mediated kinetic resolution of the racemic allenols. The substitution pattern of the aromatic ring, regarding to both the type of the substituent and its position on the aromatic ring, was found to be critical for the kinetic resolution of 1-aryl-2,3-allenols.

  20. Domain Modeling: NP_945352.1 [SAHG[Archive

    Lifescience Database Archive (English)

    Full Text Available NP_945352.1 chr9 Snow Flea Antifreeze Protein Quasi-racemate p2pnea_ chr9/NP_945352.1/NP_945352....1_apo_14-116.pdb p3boga_ chr9/NP_945352.1/NP_945352.1_holo_14-116.pdb swppa 20A,21H,23R,30L,44P

  1. 1-(4-Bromo-3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-ylethan-1-one: a precursor for phase-I metabolite of AHTN

    Directory of Open Access Journals (Sweden)

    Paul Kuhlich

    2013-04-01

    Full Text Available The title compound, C18H25BrO, crystallized as a racemate with four independent molecules in the asymmetric unit. In the crystal, three of these four molecules are linked via C—Br...Br—C halogen bonds [Br...Br = 3.662 (2 and 3.652 (2 Å], forming dimers.

  2. Enantioselective reduction of ketones and imines catalyzed by (CN-box)Re(V)-oxo complexes.

    Science.gov (United States)

    Nolin, Kristine A; Ahn, Richard W; Kobayashi, Yusuke; Kennedy-Smith, Joshua J; Toste, F Dean

    2010-08-16

    The development and application of chiral, non-racemic Re(V)-oxo complexes to the enantioselective reduction of prochiral ketones is described. In addition to the enantioselective reduction of prochiral ketones, we report the application of these complexes to 1) a tandem Meyer-Schuster rearrangement/reduction to access enantioenriched allylic alcohols and 2) the enantioselective reduction of imines.

  3. Syntheses of (±-Romucosine and (±-Cathafiline

    Directory of Open Access Journals (Sweden)

    Surachai Nimgirawath

    2006-11-01

    Full Text Available The structures previously assigned to (--romucosine and (+-cathafiline, N-(methoxycarbonyl aporphine alkaloids from Rollina mucosa (Annonaceae and Cassytha filiformis (Lauraceae respectively, have been confirmed by total syntheses of the racemic substances. The key step of the syntheses involved formation of ring C of the aporphines by a radical-initiated cyclisation.

  4. Diastereoselective Synthesis of 5-Hydroxy-8-methoxy-1-oxaspiro[5,5]undeca-7,10-diene-9-one

    Directory of Open Access Journals (Sweden)

    Thomas W. Scully

    2013-01-01

    Full Text Available A short five steps synthesis of the title compound from vanillin is described. The racemic spiroether 7 was obtained in 61% yield and in >99% diastereomeric excess (by 1H-NMR from the corresponding phenolic derivative 3 by oxidation with lead (IV acetate.

  5. Cathodic reductive coupling of methyl cinnamate on boron-doped diamond electrodes and synthesis of new neolignan-type products.

    Science.gov (United States)

    Kojima, Taiki; Obata, Rika; Saito, Tsuyoshi; Einaga, Yasuaki; Nishiyama, Shigeru

    2015-01-01

    The electroreduction reaction of methyl cinnamate on a boron-doped diamond (BDD) electrode was investigated. The hydrodimer, dimethyl 3,4-diphenylhexanedioate (racemate/meso = 74:26), was obtained in 85% yield as the major product, along with small amounts of cyclic methyl 5-oxo-2,3-diphenylcyclopentane-1-carboxylate. Two new neolignan-type products were synthesized from the hydrodimer.

  6. Influence of drug transporters and stereoselectivity on the brain penetration of pioglitazone as a potential medicine against Alzheimer's disease.

    Science.gov (United States)

    Chang, Kai Lun; Pee, Hai Ning; Yang, Shili; Ho, Paul C

    2015-03-11

    Pioglitazone is currently undergoing clinical trials for treatment of Alzheimer's disease (AD). However, poor brain penetration remains an obstacle to development of the drug for such intended clinical uses. In this study, we demonstrate that the inhibition of P-glycoprotein (P-gp) significantly increases brain penetration of pioglitazone, whereas inhibition of breast cancer resistance protein (BCRP) has little effect. We also investigate the stereoselectivity of pioglitazone uptake in the brain. When mice were dosed with racemic pioglitazone, the concentration of (+)-pioglitazone was 46.6% higher than that of (-)-pioglitazone in brain tissue and 67.7% lower than that of (-)-pioglitazone in plasma. Dosing mice with pure (+)-pioglitazone led to a 76% increase in brain exposure levels compared to those from an equivalent dose of racemic pioglitazone. Pure (+)-pioglitazone was also shown to have comparable amyloid-lowering capabilities to the racemic pioglitazone in an in vitro AD model. These results suggest that P-gp may act as a stereoselective barrier to prevent pioglitazone entry into the brain. Dosing with (+)-pioglitazone instead of the racemic mixture may result in higher levels of brain exposure to pioglitazone, thus potentially improving the development of pioglitazone treatment of AD.

  7. Enhancement of the enantioselectivity of carboxylesterase A by structure-based mutagenesis

    NARCIS (Netherlands)

    Godinho, Luis F.; Reis, Carlos R.; Rozeboom, Henriette J.; Dekker, Frank J.; Dijkstra, Bauke W.; Poelarends, Gerrit J.; Quax, Wim J.

    2012-01-01

    Previously studied Bacillus subtilis carboxylesterases (CesA and CesB) have potential for the kinetic resolution of racemic esters of 1,2-O-isopropylideneglycerol (IPG). CesA exhibits high activity but low enantioselectivity towards IPG-butyrate and IPG-caprylate, while the more enantioselective Ces

  8. [Sublicons containing amino acids and nucleotides].

    Science.gov (United States)

    Kaĭmakov, E A

    1979-01-01

    Sublicons have been obtained. Sublicons are threadlike structures appearing during sublimation of frozen solutions of small concentrations, containing racemate mixture of amino acids and nucleotides. It is suggested that close location of chains and their zonal distribution by the section of helix spire forming sublicon wall, should provide the formation of stereohomogenous and complementary successions of biomonomers of different clases.

  9. Differential psychopathology and patterns of cerebral glucose utilisation produced by (S)- and (R)-ketamine in healthy volunteers using positron emission tomography (PET)

    NARCIS (Netherlands)

    Vollenweider, FX; Leenders, KL; Oye, [No Value; Hell, D; Angst, J

    1997-01-01

    Until recently, racemic ketamine (S-ketamine/R-ketamine=50:50) has been used to study NMDA receptor hypofunction in relation to pathophysiological models of schizophrenia. Ketamine given to normal humans in subanesthetic doses produces a model psychosis including both positive and negative symptoms

  10. Enantioselective adsorption of ibuprofen and lysine in metal-organic frameworks

    NARCIS (Netherlands)

    Bueno-Perez, R.; Martin-Calvo, A.; Gómez-Álvarez, P.; Gutiérrez-Sevillano, J.J.; Merkling, P.J.; Vlugt, T.J.H.; van Erp, T.S.; Dubbeldam, D.; Calero, S.

    2014-01-01

    This study reveals the efficient enantiomeric separation of bioactive molecules in the liquid phase. Chiral structure HMOF-1 separates racemic mixtures whereas heteroselectivity is observed for scalemic mixtures of ibuprofen using non-chiral MIL-47 and MIL-53. Lysine enantiomers are only separated

  11. Chrysobalanaceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1973-01-01

    Woody plants. Leaves alternate, simple. Stipules present. Inflorescence consisting of panicles or racemes. Flowers hermaphrodite or rarely unisexual, zygomorphic; receptacle saucer-shaped or tubular. Sepals free, imbricate. Petals free, imbricate or convolute or the petals wanting. Stamens (2—) 10 t

  12. Burseraceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1984-01-01

    Trees; the inner bark always provided with resiniferous ducts. Leaves alternate, imparipinnate or 1—3-foliolate. Stipules wanting. Inflorescence consisting of raceme-like panicles. Flowers hermaphrodite or polygamodioecious, actinomorphic. Sepals 3—5, free or connate. Petals 3—5, free, deciduous. St

  13. Elaeocarpaceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1984-01-01

    Trees or shrubs. Leaves alternate, opposite, simple; petioles often thickened at both ends. Stipules present, deciduous. Inflorescence consisting of racemes or panicles or flowers solitary. Flowers actinomorphic, 4—5-merous, mostly hermaphrodite. Sepals 4—5. Petals 4—5 or wanting. Stamens numerous,

  14. Malpighiaceae

    NARCIS (Netherlands)

    Troost, P.G.H.

    1984-01-01

    Woody plants, trees, shrubs or undershrubs, often twining, with bi-branched strigae and glands on leaves and other sterile parts. Inflorescence consisting of racemes. Flowers zygomorphic. Sepals 5, sometimes all, but mostly 4 with one or two glands without. Petals 5, free, clawed and mostly with a l

  15. Tamaricaceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1966-01-01

    Shrubs, trees or rarely herbs. Leaves alternate, sessile, simple, often scale-like or needle-shaped. Stipules wanting. Flowers solitary or in spikes or racemes, actinomorphic, hermaphrodite. Sepals 4—5, free or united at base. Petals 4—5, free or nearly so, imbricate. Stamens 4 to many; filaments us

  16. Theophrastaceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1984-01-01

    Evergreen trees or shrubs. Leaves simple, coriaceous, alternate, rarely opposite, often crowded and pseudo-verticillate at the top of the branches. Stipules wanting. Inflorescence consisting of axillary or terminal racemes or flowers solitary by reduction. Flowers hermaphrodite in our species, actin

  17. Canellaceae

    NARCIS (Netherlands)

    Stoffers, A.L.

    1966-01-01

    Glabrous trees or rarely shrubs, with aromatic bark. Leaves alternate, simple, entire, pinnately veined, with pellucid dots. Stipules wanting. Inflorescence consisting of axillary or terminal cymes or racemes. Flowers hermaphrodite, actinomorphic. Sepals 3—5, imbricate. Petals 4—12, free or basicall

  18. Design, synthesis, and pharmacological characterization of novel spirocyclic quinuclidinyl-Delta2 -isoxazoline derivatives as potent and selective agonists of alpha7 nicotinic acetylcholine receptors

    DEFF Research Database (Denmark)

    Dallanoce, Clelia; Magrone, Pietro; Matera, Carlo;

    2011-01-01

    A set of racemic spirocyclic quinuclidinyl-¿(2) -isoxazoline derivatives was synthesized using a 1,3-dipolar cycloaddition-based approach. Target compounds were assayed for binding affinity toward rat neuronal homomeric (a7) and heteromeric (a4ß2) nicotinic acetylcholine receptors. ¿(2) -Isoxazol...

  19. Studies on inclusion resolution : gaining insight into chemical and physical properties

    NARCIS (Netherlands)

    Müller, Simona

    2003-01-01

    Inclusion is a process where two or more compounds crystallise together in a mixed, but regular, crystal lattice. Inclusion resolution is a relatively new way for separating enantiomers from a racemic mixture which employs inclusion with enantiopure compounds as hosts. An enantiopure host compound c

  20. Racisme - et psykologisk perspektiv

    DEFF Research Database (Denmark)

    Singla, Rashmi; Busch-Jensen, Peter

    2007-01-01

    Racisme forstås traditionelt som diskrimination og eksklusion af grupper eller individer ud fra forestillinger om, at mennesker tilhører forskellige racer, der kan rangordnes. I denne betydning indebærer racisme altså en ide om, at mennesket findes i forskellige racemæssige udgaver, karakterisere...

  1. Effects of salbutamol and enantiomers on allergen-induced asthmatic reactions and airway hyperreactivity

    NARCIS (Netherlands)

    Westerhof, Fiona; Zuidhof, A.B; Kok, L.; Meurs, Herman; Zaagsma, Hans

    2005-01-01

    Salbutamol consists of a racemic mixture of R- and S-salbutamol. R-salbutamol (levalbuterol) is the active bronchodilating enantiomer, whereas S-salbutamol is thought to be pharmacologically inactive or to exert adverse effects. This study evaluated the bronchoprotective effects of inhalation of the

  2. The Chiral Bilayer Effect Stabilizes Micellar Fibers

    NARCIS (Netherlands)

    Fuhrhop, Jürgen-Hinrich; Schnieder, Peter; Rosenberg, Jörg; Boekema, Egbert

    1987-01-01

    Dihelical fibers several micrometers in length and gels were obtained by spontaneous aggregation of octyl L- and D-gluconamides. The single strands have the thickness of a bimolecular layer. No fibers are formed from the racemate. The tendency of the chiral amphiphiles to aggregate to very long

  3. Synthesis of (+/-)-clusianone: high-yielding bridgehead and diketone substitutions by regioselective lithiation of enol ether derivatives of bicyclo[3.3.1]nonane-2,4,9-triones.

    Science.gov (United States)

    Rodeschini, Vincent; Ahmad, Nadia M; Simpkins, Nigel S

    2006-11-09

    [Structure: see text] A concise synthesis of the polyprenylated acylphloroglucinol natural product, clusianone, in racemic form, is described. An Effenburger cyclization generated a core bicyclo[3.3.1]nonane-trione structure, which was then elaborated by means of regioselective lithiation reactions.

  4. Preparation of 4- and 6-desphenyl analogues of (-)-clausenamide and alternative synthesis of (+)-epi-clausenamide

    Institute of Scientific and Technical Information of China (English)

    Jian Jun Xue; Yu Mei Zhou; Xiao Ming Yu

    2011-01-01

    4- and 6-desphenyl analogues of (-)-clausenamide, 6 and 7, were prepared in optical active form from commercially available D-pyroglutamic acid and the known racemic pyrrolidinone 13, respectively. In order to confirm the absolute stereochemistry of (+)-and (-)-7, intermediate 19b was transferred into the (+)-epi-clausenamide 8.

  5. Cloning and application of epoxide hydrolases from yeasts

    NARCIS (Netherlands)

    Visser, J.H.

    2002-01-01

    Epoxides are cyclic ethers that readily react with various nucleophilic compounds. Consequently, epoxides can be used in many chemical synthesis reactions. Two enantiomeric forms of an epoxide are possible if one of the carbon atoms is chiral. This means that the epoxide is actually a racemic mixtur

  6. Synthesis and chiral HPLC analysis of the dibenzyltetrahydrofuran lignans, larreatricins, 8'-epi-larreatricins, 3,3'-didemethoxyverrucosins and meso-3,3'-didemethoxynectandrin B in the creosote bush (Larrea tridentata): evidence for regiospecific control of coupling.

    Science.gov (United States)

    Moinuddin, Syed G A; Hishiyama, Shojiro; Cho, Man-Ho; Davin, Laurence B; Lewis, Norman G

    2003-07-07

    The creosote bush (Larrea tridentata) lignans are linked via 8-8' bonds, with the simplest apparently being E-p-anol derived. Of the latter, four of the six theoretically possible diastereoisomers were isolated, namely (-)-larreatricin, (-)-8'-epi-larreatricin, meso-3,3'-didemethoxynectandrin B and the new compounds, (+)- and (-)-3,3'-didemethoxyverrucosins. Following synthesis of each in either racemic or meso form, and chiral HPLC separation of the antipodes of the racemates, it was established that naturally occurring (-)-larreatricin and (-)-8'-epi-larreatricin were present in 92 and 98% enantiomeric excess, respectively, whereas 3,3'-didemethoxyverrucosin was essentially racemic and 3,3'-didemethoxynectandrin B was in the meso-form. The evidence suggests that formation of these lignans occurs under regiospecific, rather than stereoselective, coupling control. This contrasts with laccase-catalyzed "random" coupling of E-p-anol in vitro which generates the corresponding racemic 8-8', 8-3' and 8-O-4' linked dimeric moieties.

  7. Chirality Emergence in Thin Solid Films of Amino Acids by Polarized Light from Synchrotron Radiation and Free Electron Laser

    Directory of Open Access Journals (Sweden)

    Mashahiro Adachi

    2009-07-01

    Full Text Available One of the most attractive hypothesis for the origin of homochirality in terrestrial bioorganic compounds is that a kind of “chiral impulse” as an asymmetric excitation source induced asymmetric reactions on the surfaces of such materials such as meteorites or interstellar dusts prior to the existence of terrestrial life (Cosmic Scenario. To experimentally introduce chiral structure into racemic films of amino acids (alanine, phenylalanine, isovaline, etc., we irradiated them with linearly polarized light (LPL from synchrotron radiation and circularly polarized light (CPL from a free electron laser. After the irradiation, we evaluated optical anisotropy by measuring the circular dichroism (CD spectra and verified that new Cotton peaks appeared at almost the same peak position as those of the corresponding non-racemic amino acid films. With LPL irradiation, two-dimensional anisotropic structure expressed as linear dichroism and/or linear birefringence was introduced into the racemic films. With CPL irradiation, the signs of the Cotton peaks exhibit symmetrical structure corresponding to the direction of CPL rotation. This indicates that some kinds of chiral structure were introduced into the racemic film. The CD spectra after CPL irradiation suggest the chiral structure should be derived from not only preferential photolysis but also from photolysis-induced molecular structural change. These results suggest that circularly polarized light sources in space could be associated with the origin of terrestrial homochirality; that is, they would be effective asymmetric exciting sources introducing chiral structures into bio-organic molecules or complex organic compounds.

  8. Enantioconvergent catalysis

    Directory of Open Access Journals (Sweden)

    Justin T. Mohr

    2016-09-01

    Full Text Available An enantioconvergent catalytic process has the potential to convert a racemic starting material to a single highly enantioenriched product with a maximum yield of 100%. Three mechanistically distinct approaches to effecting enantioconvergent catalysis are identified, and recent examples of each are highlighted. These processes are compared to related, non-enantioconvergent methods.

  9. Carbamoylcholine homologs

    DEFF Research Database (Denmark)

    Jensen, Anders A.; Mikkelsen, Ivan Bisgaard; Frølund, Bente

    2004-01-01

    In a recent study, racemic 3-(N,N-dimethylamino)butyl-N,N-dimethylcarbamate (1) was shown to be a potent agonist at neuronal nicotinic acetylcholine receptors with a high selectivity for nicotinic over muscarinic acetylcholine receptors [Mol. Pharmacol. 64 (2003) 865-875]. Here we present the syn...

  10. Unprecedentedly mild direct Pd-catalyzed arylation of oxazolo[4,5-b]pyridine

    DEFF Research Database (Denmark)

    Zhuravlev, Fedor

    2006-01-01

    Pd-catalyzed C-2 arylation of oxazolo[4,5-b]pyridine proceeds efficiently at 30 degrees C and tolerates a variety of aryl halides, including derivatized amino acids for which no racemization was observed during the reaction. Experimental evidence for facile deprotonation of oxazolo[4,5-b]pyridine...

  11. Efficient Production of Enantiopure d-Lysine from l-Lysine by a Two-Enzyme Cascade System

    Directory of Open Access Journals (Sweden)

    Xin Wang

    2016-10-01

    Full Text Available The microbial production of d-lysine has been of great interest as a medicinal raw material. Here, a two-step process for d-lysine production from l-lysine by the successive microbial racemization and asymmetric degradation with lysine racemase and decarboxylase was developed. The whole-cell activities of engineered Escherichia coli expressing racemases from the strains Proteus mirabilis (LYR and Lactobacillus paracasei (AAR were first investigated comparatively. When the strain BL21-LYR with higher racemization activity was employed, l-lysine was rapidly racemized to give dl-lysine, and the d-lysine yield was approximately 48% after 0.5 h. Next, l-lysine was selectively catabolized to generate cadaverine by lysine decarboxylase. The comparative analysis of the decarboxylation activities of resting whole cells, permeabilized cells, and crude enzyme revealed that the crude enzyme was the best biocatalyst for enantiopure d-lysine production. The reaction temperature, pH, metal ion additive, and pyridoxal 5′-phosphate content of this two-step production process were subsequently optimized. Under optimal conditions, 750.7 mmol/L d-lysine was finally obtained from 1710 mmol/L l-lysine after 1 h of racemization reaction and 0.5 h of decarboxylation reaction. d-lysine yield could reach 48.8% with enantiomeric excess (ee ≥ 99%.

  12. Anti-cancer agents based on 6-trifluoromethoxybenzimidazole derivatives and method of making

    Science.gov (United States)

    Gakh, Andrei A.; Vovk, Mykhaylo V.; Mel'nychenko, Nina V.; Sukach, Volodymyr A.

    2012-08-14

    The present disclosure relates to novel compounds having the structural Formulas (1a,1b), stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof as chemotherapy agents for treating of cancer, particularly androgen-independent prostate cancer. The disclosure also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

  13. Synthesis, crystal and molecular structure and dynamic behaviour of new dimethyldioxanedione based inherently dissymmetric overcrowded alkenes.

    NARCIS (Netherlands)

    Huck, NPM; Meetsma, A; Zijlstra, R; Feringa, BL; Huck, Nina P.M.; Feringa, Bernard

    1995-01-01

    Two representatives of new chiral sterically overcrowded ethylenes, 2-methyl(9-thioxanthylidene)-2,2-dimethyl- 1,3-dioxane-4,6-dione (3) and 12H-benzo[a]thioxanthylidene-2,2-dimethyl-1,3-dioxane-4,6-dione (5), have been prepared and dynamic H-1 NMR studies revealed 1 racemization barriers of 10.3

  14. Dynamic control and amplification of molecular chirality by circular polarized light

    NARCIS (Netherlands)

    Huck, N.P.M.; Jager, W.F.; de Lange, B.; Feringa, B.L.

    1996-01-01

    The enantiomers of a racemic photoresponsive material represent two distinct states that can be modulated with irradiation at a single wavelength by changing the handedness of the light, Dynamic control over molecular chirality was obtained by the interconversion of enantiomers of helically shaped

  15. Glycerol as green solvent for efficient obtention of beta -hydroxyesters; Glicerol como solvente verde em eficiente obtencao de beta-hidroxiesteres

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Simone Santos de Sousa; Fiaux, Sorele Batista; Barreto, Igor Ramon Lomba; Muri, Estela Maris Freitas; Dias, Luiza Rosaria Sousa, E-mail: ldias@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Faculdade de Farmacia; Ramos, Maria da Conceicao Klaus V.; Aquino Neto, Francisco Radler de [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Centro de Tecnologia. Instituto de Quimica

    2014-05-15

    In this work, we report a new method for obtaining racemic β-hydroxyesters by reduction of β-ketoesters. The use of glycerol as a reactional medium in selective reduction of β-ketoesters into the corresponding alcohols was shown to be a viable and more efficient alternative compared with the conventional methodology, taking into account green chemistry prerogatives. (author)

  16. Differentiation of antiinflammatory and antitumorigenic properties of stabilized enantiomers of thalidomide analogs.

    Science.gov (United States)

    Jacques, Vincent; Czarnik, Anthony W; Judge, Thomas M; Van der Ploeg, Lex H T; DeWitt, Sheila H

    2015-03-24

    Therapeutics developed and sold as racemates can exhibit a limited therapeutic index because of side effects resulting from the undesired enantiomer (distomer) and/or its metabolites, which at times, forces researchers to abandon valuable scaffolds. Therefore, most chiral drugs are developed as single enantiomers. Unfortunately, the development of some chirally pure drug molecules is hampered by rapid in vivo racemization. The class of compounds known as immunomodulatory drugs derived from thalidomide is developed and sold as racemates because of racemization at the chiral center of the 3-aminoglutarimide moiety. Herein, we show that replacement of the exchangeable hydrogen at the chiral center with deuterium allows the stabilization and testing of individual enantiomers for two thalidomide analogs, including CC-122, a compound currently in human clinical trials for hematological cancers and solid tumors. Using "deuterium-enabled chiral switching" (DECS), in vitro antiinflammatory differences of up to 20-fold are observed between the deuterium-stabilized enantiomers. In vivo, the exposure is dramatically increased for each enantiomer while they retain similar pharmacokinetics. Furthermore, the single deuterated enantiomers related to CC-122 exhibit profoundly different in vivo responses in an NCI-H929 myeloma xenograft model. The (-)-deuterated enantiomer is antitumorigenic, whereas the (+)-deuterated enantiomer has little to no effect on tumor growth. The ability to stabilize and differentiate enantiomers by DECS opens up a vast window of opportunity to characterize the class effects of thalidomide analogs and improve on the therapeutic promise of other racemic compounds, including the development of safer therapeutics and the discovery of new mechanisms and clinical applications for existing therapeutics.

  17. Stereochemistry and neuropharmacology of a ‘bath salt’ cathinone: S-enantiomer of mephedrone reduces cocaine-induced reward and withdrawal in invertebrates

    Science.gov (United States)

    Vouga, Alexandre; Gregg, Ryan A.; Haidery, Maryah; Ramnath, Anita; Al-Hassani, Hassan K.; Tallarida, Christopher S.; Grizzanti, David; Raffa, Robert B.; Smith, Garry R.; Reitz, Allen B.; Rawls, Scott M.

    2015-01-01

    Knowledge about the neuropharmacology of mephedrone (MEPH) applies primarily to the racemate, or street form of the drug, but not to its individual enantiomers. Here, through chemical isolation of MEPH enantiomers and subsequent behavioral characterization in established invertebrate (planarian) assays, we began separating adverse effects of MEPH from potential therapeutic actions. We first compared stereotypical and environmental place conditioning (EPC) effects of racemic MEPH, S-MEPH, and R-MEPH. Stereotypy was enhanced by acute treatment (100–1000 μM) with each compound; however, S-MEPH was less potent and efficacious than racemate and R-MEPH. Both R-MEPH (10, 100, 250 μM) and racemate (100 μM) produced EPC, but S-MEPH was ineffective at all concentrations (10–100 μM). After showing that S-MEPH lacked rewarding efficacy, we investigated its ability to alter three of cocaine's behavioral effects (EPC, withdrawal, and stereotypy). Cocaine (1 μM) produced EPC that was abolished when S-MEPH (100 μM) was administered after cocaine conditioning. Spontaneous withdrawal from chronic cocaine exposure caused a reduction in motility that was not evident during acute or continuous cocaine treatment but was attenuated by S-MEPH (100 μM) treatment during the cocaine abstinence interval. Acute stereotypy produced by 1 mM cocaine, nicotine or racemic MEPH was not affected by S-MEPH (10–250 μM). The present results obtained using planarian assays suggest that the R-enantiomer of MEPH is predominantly responsible for its stimulant and rewarding effects and the S-enantiomer is capable of antagonizing cocaine's addictive-like behaviors without producing rewarding effects of its own. PMID:25496724

  18. Enantiomeric specificity in a pheromone-kairomone system of two threatened saproxylic beetles, Osmoderma eremita and Elater ferrugineus.

    Science.gov (United States)

    Svensson, Glenn P; Larsson, Mattias C

    2008-02-01

    The scarab beetle Osmoderma eremita and its larval predator, the click beetle Elater ferrugineus, are threatened saproxylic beetles regarded as indicators of the species-richness of insect fauna of hollow deciduous trees. Male O. eremita produce the pheromone (R)-(+)-gamma-decalactone to attract conspecific females, and this compound is also utilized by E. ferrugineus as a kairomone, presumably for detection of tree hollows containing prey. We have investigated enantiomeric specificity to gamma-decalactone in this pheromone-kairomone system by electrophysiological and field trapping experiments. In single-sensillum recordings from male and female O. eremita, which used the (R)-enantiomer and the racemic mixture of gamma-decalactone as odor stimuli, numerous olfactory receptor neurons (ORNs) responding to both stimuli were found. No neurons responded preferentially to the racemic mixture, showing that these beetles seem to lack receptors specific for the (S)-enantiomer. The enantiomeric specificity of ORNs was confirmed by gas chromatography-linked single-sensillum recordings where the two enantiomers in a racemic mixture were separated on a chiral column. Furthermore, in field experiments that used the (R)-enantiomer and the racemic mixture as lures, the attraction of O. eremita females corresponded to the amount of (R)-enantiomer released from lures with the (S)-enantiomer displaying no antagonistic effects. Trap catch data also suggested that the (S)-enantiomer is not a behavioral antagonist for E. ferrugineus. The odor-based system can be highly efficient in attracting the larval predator where trap catch in 1 yr almost equaled the total number of specimens collected in Sweden until 1993. Our study shows that racemic gamma-decalactone could be used for cost-effective monitoring of both beetles.

  19. D:L-AMINO Acids and the Turnover of Microbial Biomass

    Science.gov (United States)

    Lomstein, B. A.; Braun, S.; Mhatre, S. S.; Jørgensen, B. B.

    2015-12-01

    Decades of ocean drilling have demonstrated wide spread microbial life in deep sub-seafloor sediment, and surprisingly high microbial cell numbers. Despite the ubiquity of life in the deep biosphere, the large community sizes and the low energy fluxes in the vast buried ecosystem are still poorly understood. It is not know whether organisms of the deep biosphere are specifically adapted to extremely low energy fluxes or whether most of the observed cells are in a maintenance state. Recently we developed and applied a new culture independent approach - the D:L-amino acid model - to quantify the turnover times of living microbial biomass, microbial necromass and mean metabolic rates. This approach is based on the built-in molecular clock in amino acids that very slowly undergo chemical racemization until they reach an even mixture of L- and D- forms, unless microorganisms spend energy to keep them in the L-form that dominates in living organisms. The approach combines sensitive analyses of amino acids, the unique bacterial endospore marker (dipicolinic acid) with racemization dynamics of stereo-isomeric amino acids. Based on a heating experiment, we recently reported kinetic parameters for racemization of aspartic acid, glutamic acid, serine and alanine in bulk sediment from Aarhus Bay, Denmark. The obtained racemization rate constants were faster than the racemization rate constants of free amino acids, which we have previously applied in Holocene sediment from Aarhus Bay and in up to 10 mio yr old sediment from ODP Leg 201. Another important input parameter for the D:L-amino acid model is the cellular carbon content. It has recently been suggested that the cellular carbon content most likely is lower than previously thought. In recognition of these new findings, previously published data based on the D:L-amino acid model were recalculated and will be presented together with new data from an Arctic Holocene setting with constant sub-zero temperatures.

  20. Stereochemistry and neuropharmacology of a 'bath salt' cathinone: S-enantiomer of mephedrone reduces cocaine-induced reward and withdrawal in invertebrates.

    Science.gov (United States)

    Vouga, Alexandre; Gregg, Ryan A; Haidery, Maryah; Ramnath, Anita; Al-Hassani, Hassan K; Tallarida, Christopher S; Grizzanti, David; Raffa, Robert B; Smith, Garry R; Reitz, Allen B; Rawls, Scott M

    2015-04-01

    Knowledge about the neuropharmacology of mephedrone (MEPH) applies primarily to the racemate, or street form of the drug, but not to its individual enantiomers. Here, through chemical isolation of MEPH enantiomers and subsequent behavioral characterization in established invertebrate (planarian) assays, we began separating adverse effects of MEPH from potential therapeutic actions. We first compared stereotypical and environmental place conditioning (EPC) effects of racemic MEPH, S-MEPH, and R-MEPH. Stereotypy was enhanced by acute treatment (100-1000 μM) with each compound; however, S-MEPH was less potent and efficacious than racemate and R-MEPH. Both R-MEPH (10, 100, 250 μM) and racemate (100 μM) produced EPC, but S-MEPH was ineffective at all concentrations (10-100 μM). After showing that S-MEPH lacked rewarding efficacy, we investigated its ability to alter three of cocaine's behavioral effects (EPC, withdrawal, and stereotypy). Cocaine (1 μM) produced EPC that was abolished when S-MEPH (100 μM) was administered after cocaine conditioning. Spontaneous withdrawal from chronic cocaine exposure caused a reduction in motility that was not evident during acute or continuous cocaine treatment but was attenuated by S-MEPH (100 μM) treatment during the cocaine abstinence interval. Acute stereotypy produced by 1 mM cocaine, nicotine or racemic MEPH was not affected by S-MEPH (10-250 μM). The present results obtained using planarian assays suggest that the R-enantiomer of MEPH is predominantly responsible for its stimulant and rewarding effects and the S-enantiomer is capable of antagonizing cocaine's addictive-like behaviors without producing rewarding effects of its own.